JPS62243605A - Production of alpha-olefin - Google Patents

Abstract

PURPOSE:To enable long-term continuous operation of a process for the production of high-purity alpha-olefin suppressing the formation of wax, by oligomerizing ethylene using a ternary component catalyst composed of a Zr compound, an Al compound, etc. CONSTITUTION:An ethylene-containing gas is polymerized in the presence of a catalyst consisting of (A) a Zr halide of formula I (X and A are Cl, Br or I; a is 0-4) (e.g. ZrCl4, ZrBrCl3, etc.), (B) an alkyl Al of formula II (R is 1-20C alkyl; Q is Cl, Br or I) [e.g. Al2(CH3)3Cl3, etc.] or a mixture of the alkyl Al of formula II and an alkyl Al of formula III (R' and Q' are same as R and Q; b is 1-3) [e.g. Al(CH3)3, etc.] and (C) one or more S, P or N compounds (e.g. dimethyl sulfide, triphenylphosphine, methylamine, etc.).

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a method for producing linear α-olefins, and more specifically, the present invention relates to a method for producing linear α-olefins.
- A method for producing olefins that is capable of producing α-olefins with high purity, produces less wax ψ even under high-temperature reaction conditions, and is capable of producing α-olefins that can be operated continuously for a long period of time. Regarding the method.

[Prior Art and its Problems] Linear α-olefins are useful as modifying comonomers in the field of polyolefin production, or as plasticizers and surfactants when alcoholized.

Such linear α-olefins can be produced by oligomerizing ethylene in the presence of a catalyst.
Common. As the catalyst used at this time, for example, a two-component catalyst consisting of titanium tetrachloride and ethylaluminum dichloride is known. Furthermore, a method is also known in which a third component is added to this system to improve the yield of α-olefin and the J1 selectivity.

On the other hand, 1. I
- Did you use a zirconium (Zr) compound instead of the titanium compound mentioned above? Component-based catalysts have been proposed, e.g.
Unexamined Japanese Patent Publication No. 11/(58-109428, Japanese Patent Publication No. 5G-
30042 and JP-A-58-201729 disclose a two-component catalyst of a Zr compound and an AfL compound, respectively, and JP-A-58-113138 discloses a Z
2]ji and a splitting catalyst with the r compound are disclosed, respectively.

[7] However, in the method of oligomerizing ethylene using a two-component catalyst containing the above-mentioned Zr compound,
The final product will contain a very large amount of wax, or the yield of an oligomer with a small number of IRJs, for example an oligomer with about 4 carbon atoms, will be high, and the resulting α-olefin itself will be There are problems such as extremely low purity of T, and further problems such as long-term continuous operation is difficult due to the fact that T produces a large amount of wax.

[Purpose of the invention] This invention has been made based on the above circumstances.

That is, the purpose of the present invention is to solve the conventional problem (a) and provide a method for producing linear α-olefins by oligomerizing ethylene in the presence of a catalyst. It is an object of the present invention to provide a method for preparing α-olefins, which has a high yield of a fraction, has high purity of the obtained α-olefins, and further produces less wax content, and is suitable for long-term continuous operation.

As a result of intensive research in order to achieve the above-mentioned [Objective 1], the inventors discovered that when using a novel three-component catalyst comprising a Zr compound, a culture compound A, and a third component (described later), The present invention was completed based on the discovery that excellent effects can be obtained.

[Means for solving the above-mentioned problems] The outline of the present invention for solving the above-mentioned problems is as follows: often represents C1, Br, or I, respectively, and
a represents an integer of 0 to 4,) Te A
represents CQ, Br, or ■, provided that R and Q
may be different times or times, respectively. Note that the above-mentioned formula [2] can also be expressed by An2Ri Ql. ) or an alkyl aluminum compound represented by formula [2] of 11u and the following formula: % formula % [31 (wherein Ro and Qo are respectively the above-mentioned R and
Represents the α taste, similar to Q in 0, and b represents an integer from 1 to 3, provided that Ro and Qo may be the same or different.) an ethylene-containing gas in the presence of a mixture with an alkyl aluminum compound represented by This is a method for preparing α-olefins, which is characterized by polymerizing α-olefins.

That is, in the method of the present invention, the zirconium halide (hereinafter, this may be referred to as the [A] acid component) and the alkyl aluminum compound (hereinafter, this may be referred to as the [B] acid component).
] Sometimes called an acid component. ), sulfur compounds, and/or phosphorus compounds and/or nitrogen compounds (hereinafter referred to as
These compounds are sometimes called [C] acid components. ) is characterized by the use of a novel catalyst of the so-called 3J & split system, which is derived from I/li.

The zirconium halide used as the acid component [A] is not particularly limited as long as it satisfies the conditions shown in the formula [11], and specific examples include:
Zr C1a, Zr Br4゜Zr Is
, Zr Br CfL ko , Zr
Among these, ZrC15 is particularly preferred. These may be used singly or in combination of two or more.

[B] The alkylaluminum compound represented by the formula [2] used as the acid component (hereinafter referred to as [B-
1] Sometimes called ingredients. )teeth.

In the above formula [2], as long as R and Q each satisfy the above-mentioned conditions, there is no particular restriction on v1, and as a specific example, for example, AJl? (C83)3 CQI
, Ajl2 (CHl)I Br3゜A, lL/(
C7H5)3Clgo, An2CC7I5)tBr3, A
ny (C7H!l) :l It.

A12 (C2Hs)3 Br C12,Al1 (
C1H+) = CJ13, A
jl 2 (iso -Cz H+)
3Cl, Al1(C4Hq)3CJ13. Ajl7
(iso -Cs H9)3 C13,Al1 (Cs
HN) :l, AfLy (C8817) 3C
J13. Any CCy Hs)? (CH3)C
113 etc. can be mentioned. Among these, as R, a methyl group, an ethyl group, a propyl group, and a butyl group 7 are preferable, and an ethyl group is particularly preferable, and as Q,
0 sentence is preferable, specifically, ethylaluminum sesquichloride [A sentence (C7I5) t5C exchange 5,
That is, Ai2 (C2H5')3C3] can be mentioned as a suitable one. In addition, even if these alkylaluminum compounds are used alone, 2J
I! The following may be used in combination.

In the method of the present invention, the above-mentioned [B] Il&, minute and shite, the [B-11 component of section a and the above-mentioned [3]A, the alkyl aluminum compound (hereinafter referred to as [8-
2] Sometimes called ingredients. ) can be used. This [B-2] component is not particularly limited as long as Ro and Q' in the formula [31] satisfy the above conditions, and examples include, for example, An (CHz)t, A cross (C, 1H
5) 3゜An (C3HL)3, A sentence (isa-
C1H+ )i, An (C4Hq) 3, An
(iso-Cs I9) 3.

An (C5H1+) 3, A sentence (C6HI3) 1
, A (Ca)i+7) ], AJl (C2
I5) 2C1,AfL(C2](5)7 Br,A
M CCp I5)2 I.

AQ (C7) [h) C12, Ai (C2I
5) Br2. AM (C?H5)I2 etc. can be mentioned. However, among the compounds represented by the above formula [3], those in which b is 3 or 2 are preferred; in the formula [31], Ro is an ethyl group, propyl group, (
, butylno^, isobutyl group, etc. are preferred, and ethyl j, ( is particularly preferred. As Q', C2 is preferred. Specifically, for example, 1-ethylaluminum and diethylaluminium chloride are listed as preferred. These alkylaluminum compounds can be used alone or in combination with two insertions.
[B-2] Can be used as component.

One of the important points about this 111 method is that 11
The above-mentioned [B-1] component is included in the [B] component of item 11. That is, 1iiJ [B-I1 component and [B
-2] Combination with component I, 1 is usually [B-2JL
It is q! that & minute is less than 50 mol% (A B?FI), preferably less than 30 mol% (A M ), lli quasi). Delicious.

[C] A sulfur compound used as the acid component.

The phosphorus compound and nitrogen compound are not particularly limited as long as they are 41a sulfur compounds, organic phosphorus compounds, and organic nitrogen compounds, but the following can be used as appropriate.

That is, examples of the sulfur compound include dimethyl sulfide! Thioethers such as dipropyl ii, dihexyl sulfide, dicyclohexyl WL, and diphenylthioether: dinotyl dioxide [(CH3
)7 S? ], diethyl disulfide, dipropyl disulfide, dibutyl disulfide, dihexyl disulfide, dicyclohexyl disulfide, ethylmethyl disulfide, and other dialkyl disulfide compounds: thiophene, 2-methylthiophene, 3-methylthiophene, 2,3-dimethyl Thiophenes such as thiophene, 2-ethylthiophene, and pentthiophene; heterocyclic sulfur compounds such as tetrahydrothiophene and thiopyran; aromatic sulfur compounds such as diphenyl sulfur, diphenyl disulfide, methylphenyl disulfide, and methylphenyl sulfur; Sulfides such as methyl sulfide, ethyl sulfide, butyl sulfide; etc. can be mentioned.

Examples of the phosphorus compound include phosphines such as triphenylphosphine, triethylphosphine, tributylamine, tolupropylphosphine, trioctylphosphine, and tricyclohexylphosphine.

Examples of the nitrogen compound include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, decylamine, 7-niline, benzylamine, naphthylamine, dimethylamine, diethylamine,
Examples include organic amines such as dibutylamine, diphenylamine, methylphenylamine, trimethylamine, triethylamine, tributylamine, triphenylamine, pyridine, and picoline.

These compounds may be used alone or in combination of two or more.

Among the various sulfur compounds, phosphorus compounds, and nitrogen compounds, for example, dimethyl disulfide, thiophene, sulfur, triphenylphosphine, tributylphosphine,
One or more compounds selected from trioctylphosphine, aniline, etc. can be particularly preferably used.

In the method of the present invention, ethylene is produced by contacting a catalyst consisting of the [Al I & min. and the [B] acid component and the [C] acid component with an ethylene-containing gas in the presence of a suitable solvent. Polymerize (oligomerize) to form α-
Make 1 olefin.

As the solvent, 1 usually an inert solvent can be used, such as benzene,
Aromatic hydrocarbons such as toluene, xylene, chlorobenzene, ethylbenzene, dichlorobenzene, chlorotoluene, etc. or their I\logine substituted products: pentane, hexane,
Examples include aliphatic paraffins such as heptane, octane, nonane, and decane; naphthenic paraffins such as cyclohexane, xane, and decalin; and haloalkanes such as dichloroethano and dichlorobutane. Among them, benzene, toluene, xylene, and chlorobenzene are preferred;
Particularly preferred is benzene.

These solvents can be used alone or in combination.

In this invention. The blending ratio of the above [A] J&, min, [B] acid component [C] I& min and 1γI solvent is usually [Al l&, min 0.
01 to 5 mmol, preferably 0.03 to 1 mmol, [B] acid component usually 0.05 to 15 mmol, preferably 0.06 to 3 mmol, [C] acid component usually 0
．． 05 to 20 mmol, preferably 0.1 to 10 mmol when the above-mentioned acid compound is used as the [C1 & minute], and 0.05 when a nitrogen compound or phosphorus compound is used as the [C] acid component. ~5 mmol. Further, regarding the blending ratio of the [Al component and (B] 1#, min), more preferable results can be obtained by setting AfL/Zr (mole ratio) in the range of 1-15.

1i? There are no particular restrictions on the order or method of blending the [A1 component, [B] acid component, [C] acid component, and the solvent, but for example, [Al component and [81 component] may be combined individually or simultaneously. , prepare a catalyst preparation solution by dissolving an appropriate amount of catalyst and a solvent manufactured by ILJ, and prepare the catalyst #! prior to the 1R combination. A method of mixing the solution and the above-mentioned solvent of the [C] acid component and subjecting the catalyst solution to Ji151 is preferably used.

When performing 'AI' on this catalyst preparation solvent or catalyst solution,
The catalyst can be activated by heating at an appropriate temperature (usually lower than the temperature of the polymerization reaction, for example).
! Note that as the solvent in 1iii, inert solvents such as the above-mentioned solvents can be preferably used.

During the polymerization, the catalyst solution 1 can be further mixed with the solvent as necessary to adjust the concentration before use.

By bringing the thus prepared catalyst or catalyst solution into contact with an ethylene-containing gas in the presence of the solvent at a predetermined reaction temperature and reaction pressure, ethylene polymerization (oligomerization) can be efficiently carried out. can be done.

The ethylene-containing gas used for ITI includes inert gas containing ethylene, pure ethylene gas for polymerization,
An ethylene gas for polymerization such as high-purity ethylene can be used, and high-purity ethylene is preferred.

The reaction temperature during polymerization is usually 50 to 200°C,
Preferably, the reaction pressure is 100 N, 150° C., and the reaction time is usually less than 5 Kg/cni' (gauge pressure), preferably less than 25 Kg/crn'' (gauge pressure). , for about 5 minutes to 2 hours, and preferably for about 15 minutes to 1 hour.

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.

In addition, it is preferable to dry the catalyst, 2) raw materials, solvents, reaction raw materials, etc. for (9) minutes, however, if there is a trace amount of moisture,
The presence of air increases the catalyst activity and the product lf! In some cases, the selection rate may increase.

In the following, 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, in an inert gas atmosphere such as argon or nitrogen, I
After dissolving 3 minutes of AlI and the [B]IA portion of the ethylaluminum sesquichloride rod in the above solvent of benzene), the mixture was heated at 60 to 80°C for 10~ while stirring! 20
Prepare the catalyst preparation solution by heating for 1 minute.

A part of this catalyst preparation solution was added in the inert gas atmosphere,
The mixture is introduced into another container equipped with a stirrer, diluted with the above-mentioned solvent such as benzene, and the above-mentioned [C]m such as thiophene is added at around room temperature and stirred to prepare a catalyst solution. By preparing the catalyst in this way, a complex catalyst of zirconium tetrachloride T, a zirconium halide and an alkylaluminum compound is formed, and the yield of the product to be lI and the purity of the linear α-olefin can be improved. 1-.

Next, under an inert gas atmosphere, add 50 to 60% of the catalyst solution.
The catalyst solution is introduced into a reactor maintained at 0° C. by pressure transport, and while stirring the catalyst solution, a gas containing ethylene such as high-purity ethylene is introduced and oligomerized under the above reaction conditions.

After a predetermined period of time has elapsed, one reaction can be terminated by adding a conventional catalyst deactivator, such as an aqueous alkali solution or an aqueous methanol solution containing an alkali, to the reaction system.

The reaction product liquid obtained by such a method contains about 6 to 44 carbon Aa, especially linear α in the range of C6 to C2o.
- Contains a high fraction of olefins.

On the other hand, the wax by-product is! It is suppressed in an A-like way.

The reaction product solution is subjected to, for example, washing with wood etc., extraction,
l&! Conventional post-treatment steps such as separation by filtration and drying steps are performed to recover the target product, a highly pure linear α-olefin, with high efficiency.

That is, by the method of this invention, the number of carbon atoms is reduced from 6 to 2.
It is possible to stably obtain a linear α-olefin with a high purity in the range of about 1.5 parts in a high yield and high selectivity. It is also possible to adjust the carbon number distribution of the product to a narrower range by selecting reaction conditions, catalyst composition, and concentration of 1fhJ.

Furthermore, when ethylene is reacted with the catalyst system used in the method of this invention, there is little wax by-product even if the reaction is carried out at a high temperature of 100°C or higher.The reason for this is not clear at this stage. However, since an alkyl aluminum sesquihalide such as ethyl aluminum sesquichloride or an alkyl aluminum compound containing this is used as the alkylaluminum compound, this reduces the degree of reduction of zirconium halides such as zirconium tetrachloride, This is thought to be to suppress the formation of polymer 6:polymer even at high temperatures. In addition, by performing the reaction at high temperature, the generated wax can be dissolved and the operation can be performed in a homogeneous solution state, and the wax does not adhere to the reactor etc., and the sustainability of the catalyst activity is good. ,
Long-term continuous operation can be performed without any problems.

In addition, 1 recovered unreacted ethylene or.

The low-boiling fraction containing this can be used as it is, or after purification, it can be recycled and used as part of the reaction raw material.The linear α-olefin produced by this IJJ method is It can be suitably used as a comonomer for the production of various copolymers, and in the fields of the divine f industry such as plasticizers and surfactant raw materials.

[Effects of the invention 1 According to this invention, the following effects can be achieved.

In the method of this invention, zirconyl tetrachloride t, 5
A novel catalyst composed of a zirconium halide, an alkyl aluminum sesquichloride such as ethyl aluminum sesquichloride, or an alkyl aluminum compound containing the same, and a specific tertiary compound, i.e., a nitrogen compound, a sulfur compound, or a phosphorus compound. system, it is possible to efficiently oligomerize ethylene. Catalytic activity for oligomerization of ethylene is 4 (,C6
The selectivity and yield of linear α-olefins in the middle distillate of about C70 are high, and highly pure linear α-olefins can be obtained efficiently.

Moreover, even if the reaction is carried out at high temperatures, there is little wax content as a by-product, and the operability of the process is significantly improved.
NF is capable of long-term continuous operation.

That is, according to the present invention, in a method for oligomerizing ethylene to produce a linear α-olefin as a middle distillate, it is possible to provide a method that is significantly superior in terms of production χL compared to conventional methods.

[Example] (Example 1-15) Catalyst Preparation Example (31!1) 50 mmol of anhydrous zirconium tetrachloride and 472 mM of dried benzene were introduced into a 1000 m flask with a stirrer under an argon atmosphere. and stirred for 30 minutes. To this, the alkylaluminum compounds shown in Table 1 are added in a molar ratio calculated from zirconium tetrachloride: 1. For example, Example 1
~4,6~10, the molar ratio (AJI (Cy
Since Hs )+5/Zr C1s was 5.0, 250 mmol of ethylaluminum sesquichloride was added. ) and stirred at SO ℃ for 30 minutes to prepare a catalyst aliment solution.

Next, a predetermined amount of benzene dried under an argon atmosphere and the catalyst 2]1 solution were introduced into a 500 ml flask, and zirconium tetrachloride, the indicated ethylaluminum compound, and benzene were added. AS was carried out so that each of the ingredients became as indicated.To this, one indicated amount of the third component (thiophene, aniline, thiourea, triphenylphosphine, or trioctylphosphine) was added as indicated in 1. , and stirred at room temperature for 10 minutes to prepare a catalyst solution.

XL''' Example of Olefin (Oligomerization of Ethylene) The catalyst solution prepared in the above catalyst preparation example was introduced into an autoclave equipped with a stirrer under a dry argon atmosphere by pumping argon. At this time, The temperature of the autoclave was maintained at 50 to 80°C. After the catalyst solution had finished weighing down, stirring was started and high purity ethylene gas was introduced into the autoclave so that the pressure reached the indicated reaction pressure. The reaction temperature was then raised to a temperature indicated at 1. Ethylene was continued to be introduced as necessary to maintain the above pressure.The reaction was continued for 1 hour while maintaining these reaction conditions. After this, the reaction was terminated by inactivating the catalyst by injecting an aqueous sodium hydroxide solution into the autoclave.The post-treatment process is as follows.

First, in one reaction product, 8J in a gas chromatography
20g of standard undecane was added, and then the wax content was filtered off using filter paper. The wax content of filter paper-L was washed with benzene f-min, and the light content in the wax was dropped into the filtrate. The reaction product of the filtrate was washed twice with 500+nJl of pure water and then dried over anhydrous potassium carbonate.

'I! obtained in this way! The clear reaction product solution was analyzed by gas chromatography. Is the distance between the stations of the product within? Se! Obtained according to quasi-law.

-・The separated wax is air-dried and then pressurized to ゛20
After drying in an alpha dryer at mmHg, the distance between the nails was measured.

In addition, #l was calculated from the Schulz Φ Flory distribution because losses for the 04 to C3 WI portion were unavoidable due to operational reasons.

The results are summarized in Table 1.

(Comparative Examples 1 to 5) Comparative Examples 1 to 5 were carried out in the same manner as in the Examples without using at least one of zirconium tetrachloride, ethylaluminum sesquichloride, and the 31st compound as shown. However, the use of each component, reaction conditions, etc. are as shown in 2. Results 1 are summarized in Table 1.

Claims (13)

[Claims] (1) The following formula: ZrX_aA_a_-_a[1] (wherein, X and A may be the same or different and each represents Cl, Br, or I. Also,
a represents a number from 0 to 4. ) and a zirconium halide represented by the following formula: AlR_1_. _5Q_1_. _5 [2] (In the formula, 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 above formula [2] is AR_7R_3Q_
It can also be represented by 3. ) or an alkyl aluminum compound represented by the above formula [2] and the following formula: AlR'_bQ'_3_-_b[3] (wherein R' and Q' are respectively the above R and the above Represents the same meaning as Q.Also, b represents an integer from 1 to 3.However, R' and Q' may be the same or different.) A gas containing ethylene is polymerized in the presence of a mixture with an alkyl aluminum compound and one or more compounds selected from the group consisting of sulfur compounds, phosphorus compounds, and nitrogen compounds. A method for producing α-olefin. (2) The method for producing an α-olefin according to claim 1, wherein the zirconium halide is zirconium tetrachloride. (3) The method for producing an α-olefin according to claim 1 or 2, wherein R and/or R' are ethyl groups. (4) α according to any one of claims 1 to 3, wherein the Q and/or Q' is Cl.
- A method for producing olefins. (5) The method for producing an α-olefin according to any one of claims 1 to 4, wherein the alkyl aluminum compound represented by the formula [2] is ethyl aluminum sesquichloride. (6) The method for producing an α-olefin according to any one of claims 1 to 5, wherein the alkyl aluminum compound represented by formula [3] is diethylaluminum chloride or triethyl aluminum. . (7) The method for producing an α-olefin according to any one of claims 1 to 6, wherein the sulfur compound is dialkyl disulfide, thioether, thiophene, or thiourea. (8) The method for producing an α-olefin according to claim 7, wherein the dialkyl disulfide is dimethyl disulfide. (9) α according to any one of claims 1 to 8, wherein the phosphorus compound is a phosphine.
- A method for producing olefins. (10) The method for producing an α-olefin according to claim 9, wherein the phosphine is triphenylphosphine, tributylphosphine, or trioctylphosphine. (11) α according to any one of claims 1 to 10, wherein the nitrogen compound is an amine.
- A method for producing olefins. (12) The method for producing an α-olefin according to claim 1, wherein the amine is aniline. (13) The method for producing α-olefin according to any one of claims 1 to 12, wherein the ethylene-containing gas is high-purity ethylene.