JPH0710780A - Production of olefin having double bond at molecular chain terminal - Google Patents

Abstract

PURPOSE:To provide a method for producing the subject olefin, without accompanying production of a string-like tacky polymer substance as a by-product in trimerization reaction and thereby capable of extremely smoothly carrying out the reaction. CONSTITUTION:In a method for producing an olefin having a double bond at one molecular chain terminal by subjecting at least one kind of monomer selected from a group consisting of ethylene, propylene and 1-butene to trimerization, this method for producing olefin having double bond at the molecular chain terminal is to use a catalytic system containing at least chromium- containing compound and an aluminum-containing compound and add hydrogen to a trimerization reactional system.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an olefin having a double bond at the end of a molecular chain. More specifically, the invention relates to ethylene, propylene and 1-
A method for producing an olefin having a double bond at one molecular chain end by trimerizing at least one compound selected from the group consisting of butenes, which is a string-like adhesive polymer substance during trimerization reaction. Therefore, the present invention relates to a method in which the reaction can be carried out extremely smoothly without the by-product of.

[0002]

2. Description of the Related Art As a method for producing an olefin having a double bond at one molecular chain terminal such as 1-hexene by trimerizing an olefin such as ethylene, the following method is known. That is, Japanese Patent Fairness 4-
Japanese Patent No. 66457 discloses a method in which a hydrolysis product of a chromium compound, an aluminum compound and a reaction product of a donor ligand are used as a catalyst. Further, JP-A-3-128904 discloses a method using a chromium-containing complex compound and an aluminum compound.
However, in these methods, a string-like sticky polymer substance is by-produced during the trimerization reaction, and the sticky polymer substance grows by adhering to the inner wall of the reactor, stirring blades, piping, etc. There was a problem that the smooth progress was hindered and the reaction could not be continued at last.

[0003]

In such a situation,
The problem to be solved by the present invention is a method for producing an olefin having a double bond at one molecular chain end by trimerizing at least one compound selected from the group consisting of ethylene, propylene and 1-butene. However, it is to provide a method capable of carrying out the reaction extremely smoothly without the by-product of the stringy sticky polymer substance during the trimerization reaction.

[0004]

The present inventors have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention, in the method for producing an olefin having a double bond at one molecular chain end by trimerizing at least one monomer selected from the group consisting of ethylene, propylene and 1-butene, The present invention relates to a method for producing an olefin having a double bond at a molecular chain end, which comprises using a catalyst system containing at least the following (A) and (B) and adding hydrogen to a trimerization reaction system. . (A) Chromium-containing compound (B) Aluminum-containing compound

The details will be described below. The present invention uses, as a raw material, at least one monomer selected from the group consisting of ethylene, propylene and 1-butene, and an olefin having a double bond at one molecular chain end by the trimerization reaction (hereinafter, referred to as “terminal olefin”). May be referred to as "."). Examples of the olefin having a double bond at one terminal of the molecular chain include 1-hexene, nonene, dodecene and the like.

In the present invention, a catalyst system containing (A) a chromium-containing compound and (B) an aluminum-containing compound is used.

Preferred chromium-containing compounds (A) have the general formula CrX _m (X represents a carboxylic acid residue, a 1,3-diketone residue, a halogen atom or an alkoxyl group,
m represents an integer of 2 to 4. The compound represented by these can be mentioned. The carboxylic acid residue has 1 to 1 carbon atoms.
20 are preferable, for example, 2-ethylhexanoic acid, naphthenic acid, acetic acid, oxy-2-ethylhexanoic acid, dichloroethylhexanoic acid, acetylacetonic acid,
Residues such as butyric acid, neopentanoic acid, lauric acid, stearic acid and oxalic acid can be mentioned. The 1,3-diketone residue is preferably one having 1 to 20 carbon atoms, and examples thereof include residues of acetylacetone and 2,2,6,6-tetramethyl-3,5-heptanedione. The halogen atom is preferably chlorine, bromine, iodine or fluorine. The alkoxyl group has 1 to 2 carbon atoms.
It is preferably 0, and examples thereof include a t-butoxy group and an i-propyl group. Specific examples of (A) include chromium (III) tris (2-ethylhexanoate), chromium (II) bis (2-ethylhexanoate), chromium (III) tris (naphthenate), and chromium (II). Bis (naphthenate), Chromium (III) Tris (acetate), Chromium (II) Bis (acetate), Chromium
(III) Tris (acetylacetonate), chromium (II)
Examples thereof include bis (acetylacetonate), chromium (III) tris (2,2,6,6-tetramethyl-3,5-heptanedionate), and chromium (IV) tetra (t-butoxide). Among them, chromium (III) tris (2-ethylhexanoate), chromium (II) bis (2-ethylhexanoate), chromium (III) tris (naphthenate), chromium (II) bis (naphthenate), chromium (IV) (t-butoxide) and the like are preferable.

Another preferred (A) chromium-containing compound
As a product, it is disclosed in JP-A-3-128904.
Compounds Containing Chromium, ie Chemical Formula Cr_Five(C_Four
H_FourN)_Ten(C_FourH₈O)_FourHaving a chemical formula
[Cr (C_FourH_FourN)_Four] [Na]₂・ 2 (OC
_FourH₈A compound having the chemical formula [Cr (C_FourH_FourN)
_Five(OC_FourH₈)] [Na]₂・ 4 (OC_FourH₈) Have
Compound, chemical formula Cr (NC _FourH_Four)₃Cl (CH₃
O (CH₂)₂OCH₃)₃Compounds containing Na and
Compounds having these compounds supported on an inorganic oxide, structure [C
r (C_FourH_FourN)_Four], A structure [Cr
(C_FourH_FourN)_Five(OC_FourH₈)] Containing a compound,
Structure Cr (NC_FourH_Four)₃Cl (CH₃O (CH₂)₂
OCH₃) -Containing compound and the compound
Obtained by contacting an activating compound which is a Lewis acid or Lewis acid
And other compounds.

The preferred aluminum-containing compound (B) is represented by the general formula AlR _n Y _3-n (R represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom, Y represents a halogen atom, and n represents 0 to 3). The alkyl aluminum compound represented by Specific examples of the alkylaluminum compound include triisobutylaluminum, tricyclohexylaluminum, diisobutylaluminum hydride, triethylaluminum, trimethylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, and ethylaluminum chloride. Among them, triethyl aluminum, triisobutyl aluminum,
Diisobutylaluminum hydride and the like are preferred.

As another preferable (B) aluminum-containing compound, the aluminum-containing compound disclosed in Japanese Patent Publication No. 4-66457, that is, the above general formula Al is used.
R _n Y _3-n to 1 mol of the compound represented by may be mentioned compounds obtained by partial hydrolysis with 1.0 to 1.1 moles of water. Specific examples of the compound include triisobutylaluminum, trihexylaluminum, diisobutylaluminum hydride, dihexylaluminum hydride, isobutylaluminum dihydride, hexylaluminum dihydride, diisobutylhexylaluminum, isobutyldihexylaluminum, trimethylaluminum, triethyl. Aluminum, tripropyl aluminum, triisopropyl aluminum, tri-
n-butyl aluminum, trioctyl aluminum,
Tridecyl aluminum, tridodecyl aluminum,
Mention may be made of tribenzylaluminum, triphenylaluminium, trinaphthylaluminium and tritolylaluminum. Examples of preferable hydrocarbyl aluminum include triisobutyl aluminum, trihexyl aluminum, diisobutyl aluminum hydride and dihexyl aluminum hydride.

As the catalyst system, a nitrogen-containing heterocyclic compound having (C) a pyrrole ring structural unit and / or an imidazole ring structural unit in addition to (A) a chromium-containing compound and (B) an aluminum-containing compound, or (D) It is preferable to contain one kind of compound selected from the group consisting of alkylisonitrile, amine and ether. Specific examples of (C) include pyrrole, 2,5-dimethylpyrrole,
1-methylpyrrole, 2-methylpyrrole, 3-methylpyrrole, 3-octylpyrrole, 3-heptylpyrrole, 2-ethylpyrrole, 2,3,4,5-tetramethylpyrrole, 3-ethyl-2,4- Dimethylpyrrole,
Examples thereof include indole, 4,5,6,7-tetrahydroindole, carbazole and imidazole. Among them, pyrrole, 2,5-dimethylpyrrole, 3-octylpyrrole, 3-heptylpyrrole and the like are preferable. Specific examples of (D) include 1,2-dimethoxyethane, diglyme, triglyme, tetrahydrofuran, veratrol, t-butylisonitrile, tetramethylethyleneamine, 1,2-diethoxyethane, tetraglyme, 1,2-dimethoxy. Propane, 2,3-dimethoxybutane, o-diethoxybenzene, methylisonitrile, ethylisonitrile, phenylisonitrile,
Examples thereof include p-tolylisonitrile and tetraethylethylenediamine. Of these, 1,2-dimethoxyethane, diglyme, triglyme, t-butylisonitrile, tetrahydrofuran, veratrol and the like are preferable.

In the present invention, the compound represented by the general formula CrX _m is used as (A), the compound represented by the general formula AlR _n Y _3-n is used as (B), and It is preferable to use the nitrogen-containing heterocyclic compound having the (C) pyrrole ring structural unit and / or the imidazole ring structural unit. As a result, in addition to the feature of the present invention that the reaction can be carried out extremely smoothly without the by-product of the stringy sticky polymer substance during the trimerization reaction, the activity, the selectivity, and the ease of preparation It is possible to add the excellent characteristic that it is a catalyst system having excellent properties and storability, and that it is not necessary to use a large amount of aluminum compound as a catalyst.

The use ratio (molar ratio) of (A) / (B) is
1/1 to 1/200 is preferable, and 1/1 is more preferable.
~ 1/50.

(C) or (D) is 1 per mol of (A)
It is preferably used in an amount of from 190 to 190 mol, more preferably 1
~ 90 mol. If the amount of (C) is too small, the selectivity of the terminal olefin may decrease. When both (C) and (D) are used, the above-mentioned usage amount is based on the total amount of (C) and (D).

To prepare the catalyst system of the present invention, for example, (A) and (B), and optionally (C), in a hydrocarbon-based solvent under an atmosphere of an inert gas such as nitrogen or argon.
Alternatively, (D) may be stirred and dissolved. Examples of the hydrocarbon solvent include pentane, hexane, heptane, 1-hexene, 1-octene, toluene, xylene and the like.

The trimerization reaction of the present invention is carried out by using the above catalyst system and adding hydrogen to the trimerization reaction system. The amount of hydrogen used is such that the concentration of hydrogen (gas) in at least one monomer selected from the group consisting of ethylene, propylene and 1-butene and hydrogen is usually 0.1 to 50 mol%, preferably 1 to 25. Adjust to be mol%.
If the amount of hydrogen is too small, the effect of suppressing the by-product of the string-like adhesive polymer substance may be insufficient, while if the amount of hydrogen is too large, the activity of the catalyst may be reduced or 1-hexene may be formed. This may cause a decrease in selectivity.

The trimerization reaction of the present invention is carried out, for example, as follows. That is, a pressure-resistant reaction vessel was charged with a catalyst system and an aliphatic hydrocarbon solvent, then at least one monomer and hydrogen selected from the group consisting of ethylene, propylene and 1-butene were introduced, and the temperature was raised. All you have to do is react. The amount of the catalyst system used is set so that the concentration of chromium atoms in the reaction solution is preferably 0.000001 to 0.05 mol / l, and more preferably 0.0001 to 0.01 mol / l. If the amount of the catalyst system used is too small, the activity may be insufficient. The reaction temperature is usually 20 to 2
The temperature is 00 ° C, preferably 60 to 100 ° C. If the reaction temperature is too low, the activity will be low, while if the reaction temperature is too high, the selectivity of the terminal olefin may be low. The reaction pressure is usually atmospheric pressure to 100 kg / cm ² , preferably 10 to 70 kg / cm ² . If the reaction pressure is too low, the activity may be insufficient. The reaction time is usually 0.1 to 8 hr, preferably 0.5 to 4 hr. If the reaction time is too short, the reaction rate may decrease. In order to separate and recover the desired terminal olefin from the reaction mixture of the present invention, a method such as distillation is used.

[0018]

EXAMPLES The present invention will be described below with reference to examples. Example 1 In a heptane solvent at room temperature under an atmosphere of argon, 82 m of (A) chromium (III) tris (2-ethylhexanoate) was added.
g (0.17 mmol), (B) triethylaluminum 0.2 g (1.76 mmol) and (C) pyrrole 7
7 mg (1.14 mmol) was stirred and dissolved to obtain a catalyst system. Next, the above catalyst system and the heptane solvent were charged into a pressure resistant reactor having an internal volume of 0.5 l, and then ethylene and hydrogen were introduced. The hydrogen (gas) concentration in ethylene and hydrogen was adjusted to 3.2 mol%.
Further, the temperature was raised with stirring to carry out a trimerization reaction. The reaction temperature was 80 ° C., the reaction pressure was 30 kg / cm ^2, and the reaction time was 2 hours. The reaction mixture is subjected to solid-liquid separation, the amount of polymer produced is determined from the weight of the solid, the liquid phase is analyzed by gas chromatography to determine the amount of product, and the produced polymer substance is measured as shown in Table 1. did.
The conditions and results are shown in Table 1.

Examples 2 and 3 and Comparative Examples 1 and 2 Example 1 was repeated except that the conditions shown in Table 1 were used. The conditions and results are shown in Table 1. In all of the examples, the produced polymers were powdery and non-tacky, and did not hinder the reaction. On the other hand, in all Comparative Examples, the produced polymer was string-like and sticky, and adhered and grew on the inner wall of the reactor, stirring blades, piping, etc., and hindered the smooth progress of the reaction.

[0020]

[Table 1] ------------------------------------------ Examples Comparative Examples Actual Examples Comparative Examples 1 1 2 3 2 Catalyst (A) * 1 Cr (III) Cr (III) Cr (III) Cr (III) Cr (III) (B) * 2 TEAL TEAL PIBAO PIBAO PIBAO (C) * 3 PROL PROL DME DME DME ( A) / (B) / (C) 1/10/7 1/11/7 1/73/22 1/63/19 1/63/18 Molar ratio Hydrogen content mol% 3.2 0 19.1 4.8 0 Reaction temperature ℃ 80 80 80 80 80 Reaction pressure kg / cm ² 30 30 20 20 20 Reaction time hr 2 2 2 2 2 Results Activity g / g-Cr * 4 1498 2020 1270 2294 2552 Selectivity% * 5 1-Hexene 83 78 80 82 80 Polymer 1.6 1.3 16 16 18 Polymer properties * 6 Powder String-like powder Powder string-like polymer [η] * 7 0.96 4.93 0.3 * 9 5 Molecular weight of polymer 10 ⁴ * 8 3 25 2 * 9 30 −−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−

* 1 (A) Cr (III): Chromium (III) tris (2-ethylhexanoate) * 2 (B) TEAL: triethylaluminum PIBAO: polyisobutylaluminoxane * 3 (C) PROL: pyrrole DME: 1,2-Dimethoxyethane * 4 Activity: Total product (1-hexene, polymer, etc.) per gram of chromium atom of catalyst (g)

* 5 Selectivity 1-Hexene: amount of 1-hexene produced (g) / total amount of product (g) × 100 Polymer: amount of polymer produced (g) / total amount of product (g) ×
100 * 6 Properties of polymer Powder: Polymer substance in powder form, not sticky. String form: Polymer substance in string form, sticky. * 7 Polymer [η]: Intrinsic viscosity of polymer * 8 Molecular weight of polymer : Approximate molecular weight of polymer estimated from intrinsic viscosity of polymer * 9 Not measured

[0023]

As described above, according to the present invention, by trimerizing at least one compound selected from the group consisting of ethylene, propylene and 1-butene,
A method for producing an olefin having a double bond at one molecular chain end, which does not accompany a stringy sticky polymer substance as a by-product during the trimerization reaction, and therefore can perform the reaction extremely smoothly. Could be provided.

Claims (4)

[Claims] 1. A method for producing an olefin having a double bond at one molecular chain end by trimerizing at least one monomer selected from the group consisting of ethylene, propylene and 1-butene, A method for producing an olefin having a double bond at a molecular chain end, which comprises using a catalyst system containing the following (A) and (B) and adding hydrogen to a trimerization reaction system. (A) Chromium-containing compound (B) Aluminum-containing compound 2. The concentration of at least one monomer selected from the group consisting of ethylene, propylene and 1-butene, and the concentration of hydrogen (gas) in hydrogen is 0.1 to 50 mol%.
The method of claim 1, wherein 3. The method according to claim 1, wherein at least one monomer selected from the group consisting of ethylene, propylene and 1-butene is ethylene. 4. The catalyst system is represented by the general formula CrX _m (X represents a carboxylic acid residue, a 1,3-diketone residue, a halogen atom or an alkoxyl group, and m represents an integer of 2 to 4). Represented by the general formula AlR _n Y _3-n (R represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom, Y represents a halogen atom, and n represents a real number from 0 to 3). 2. The method according to claim 1, which comprises a nitrogen-containing heterocyclic compound having a pyrrole ring structural unit and / or an imidazole ring structural unit.