JPH0617324B2 - Method for producing 3-methylbutene-1 - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing 3-methylbutene-1 which is a raw material of a useful polymer.

[Conventional technology]

Conventionally, it is known that 3-methylbutene-1 is produced by partial hydrogenation of isoprene. However, when isoprene is catalytically hydrogenated, in most cases, paraffin (2 -Methylbutane). Even when partial hydrogenation of hydrogenating only one double bond was successful, the main component was hydrogenated 2-methylbutene-2, which is a 1,4-adduct, or a double bond with less steric hindrance. 2-
Methylbutene-1 and the desired 3-methylbutene-1
The generation ratio of is very small.

The relatively good selectivity resulting example partially hydrogenated by 3-methylbutene-1 of isoprene, _{^{(b) Co (CN) ▲ 3- 5}} ▼ method according catalyst (ORa inter et al,
Bull. Chem. Soc. Jpn, 45 , 2723
(1972)), _{(ii) CoBr (PPh 3) 3 -BF} 3 · OEt 2 method by the catalyst (Mizorogi et, Chem.Lett., 847
(1976)), and (C) PdCl ₂ (PPh ₃ ) ₂ -SnCl ₂ catalyst method (Itaya et al., Ind. Eng. Chem. Pro.
d. Res. Dev. 11 , No. 2, 146 (197)
2)) etc. are known.

[Problems to be solved by the invention]

However, among these methods, the methods (a) and (c) do not have sufficiently high selectivity for 3-methylbutene-1, and the method (b) has insufficient reaction rate and catalytic activity. It is not enough to be used effectively.

On the other hand, there is a method of partially hydrogenating isoprene in the presence of a catalyst composed of a cobalt compound-phosphorus compound-organoaluminum compound (Japanese Patent Publication No. 45-22322), but the production ratio of 3-methylbutene-1 is at most 15%. is there.

Moreover, among these, even in a reaction system having a high selectivity for 3-methylbutene-1, the isomerization reaction of the produced 3-methylbutene-1 abruptly occurs when the reaction rate of isoprene becomes high, and as a result, the main component is It has the drawback of becoming 2-methylbutene-2. This means that when the reaction rate of isoprene increases, the amount of isoprene present in the system decreases, and 3-methylbutene-1 coordinates to the catalyst in place of isoprene, and 2-methylbutene-1 of 3-methylbutene-1.
It is considered that the isomerization reaction to 2 occurs preferentially.
On the other hand, when the reaction rate of isoprene is low, a larger amount of isoprene is present, and it is considered that isoprene is coordinated with the catalyst and the hydrogenation reaction of isoprene occurs preferentially.

[Means for solving problems]

The present inventors have conducted a partial hydrogenation reaction of isoprene to give 3-methylbutene-1 at a high selectivity and at a high reaction rate.
As a result of earnest studies to find a catalyst system and reaction conditions capable of maintaining a high selectivity of 3-methylbutene-1 even at a high isoprene reaction conversion rate, which is produced at a high reaction rate, the present invention has reached the present invention. .

That is, the present invention is a method for producing 3-methylbutene-1 by partial hydrogenation reaction of isoprene in the presence of a catalyst composed of a cobalt compound, an organic phosphine compound and an aluminum compound, wherein an acetylene compound is present in the reaction system. And a method for producing 3-methylbutene-1, wherein isoprene is partially hydrogenated in the presence of a catalyst comprising a cobalt compound, an organic phosphine compound, an aluminum compound and a boron halide compound and / or a protic acid having a pka of 1 or less. Reaction of 3-methylbutene-1
A method for producing 3-methylbutene-1 characterized in that an acetylene compound is present in the reaction system.

Hereinafter, the present invention will be described in more detail.

In the process of the invention, a catalyst system consisting of a cobalt compound, an organic phosphine compound and an aluminum compound is used.

As the cobalt compound, cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt carbonate, cobalt acetate, cobalt formate, cobalt naphthenate, cobalt oleate,
Salts of cobalt octoate, cobalt cyanide, cobalt fluoride, cobalt bromide, cobalt iodide, etc .; chelate compounds of bis (acetylacetonato) cobalt, tris (acetylacetonato) cobalt, etc .; chlorotris (triphenylphosphine) Examples thereof include organic phosphorus compound complexes such as cobalt, bromotris (triphenylphosphine) cobalt, dichlorobis (triphenylphosphine) cobalt, and dibromobis (triphenylphosphine) cobalt.

Examples of the organic phosphine compound include triphenylphosphine, tris (p-methoxyphenyl) phosphine, tris (o-methoxyphenyl) phosphine, tris (p-trimethylsilylphenyl) phosphine, tri-p-tolylphosphine. And triarylphosphines such as tri-o-tolylphosphine; tri-n-butylphosphine, tri-n-propylphosphine, tri-iso
-Trialkylphosphines such as propylphosphine; triaralkylphosphines such as tribenzylphosphine;
Diphenyl-n-propylphosphine, diphenyl-i
Mixed alkylaryl phosphines such as so-propylphosphine, 1-diphenylphosphino-2-trimethylsilylethane, 1,2-bis (diphenylphosphino) ethane; polymer phosphines such as crosslinked oligomers of triphenylphosphine Etc.

Further, as the organoaluminum compound, trimethylaluminum, triethylaluminum, tri-is
o-butyl aluminum, tri-n-butyl aluminum, tri-n-propyl aluminum, tri-n-hexyl aluminum, diethyl aluminum hydride, di-iso-butyl aluminum hydride, diethyl aluminum chloride, di-iso-butyl aluminum chloride, Organic aluminum compounds such as diethyl aluminum bromide, ethyl aluminum dichloride, iso-butyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum sesquichloride, iso-butyl aluminum sesquichloride, ethyl aluminum nisesquipromide; aluminum chloride, aluminum bromide, etc. Inorganic aluminum compounds and the like.

As the aluminum compound, it is preferable to use the organic aluminum compound and the inorganic aluminum compound described above in combination, or to use a plurality of organic aluminum compounds in combination. Further, it is more preferable to use an aluminum compound containing a halogen atom, that is, an organic aluminum compound or an inorganic aluminum compound containing a halogen atom, and an organic aluminum compound containing no halogen atom in combination.

In the present invention, it is effective to further use a boron halide compound and / or a protonic acid having a pKa of 1 or less as a catalyst component.

Examples of the boron halide compound include boron trifluoride,
Boron trichloride, boron tribromide, hydrofluoric boron trifluoride etherate _(BF 3 .OEt _2), three Hutu boron and secondary methanol product _(BF 3 · _2CH 3 OH), and the like.

Further, as the proton acid having a pKa of 1 or less, inorganic protonic acids such as sulfuric acid, hydrochloric acid, hydrobromic acid, nitric acid, phosphoric acid, perchloric acid, tetrafluoroboric acid and thiocyanic acid; trifluoroacetic acid, trichloroacetic acid, trichloromethane Organic protic acids such as sulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid can be used. Among the above, the organic protonic acid is more preferably used.

Further, in the present invention, an acetylene compound is allowed to exist in the reaction system.

Specifically, acetylene, propyne, 1-butyne, 2-
Butyne, 1-pentine, 2-pentine, 1-hexyne,
2-hexyne, 3-hexyne, 1-heptin, 2-heptin, 3-heptin, 1-octyne, 2-octyne, 3
-Octyne, 4-octyne, 1-nonine, 2-nonine,
3-nonine, 4-nonine, 1-decine, 3-decine, 4
-Straight chain acetylenic hydrocarbons such as decyne; 3,3-
Alkylacetylenes such as dimethylbutyne-1,2,2,5,5-tetramethylhexyne-3; arylacetylenes such as phenylacetylene and diphenylacetylene; silylacetylenes such as trimethylsilylacetylene and bis (trimethylsilyl) acetylene And the like.

The cobalt compound is 1 mol of raw material isoprene,
The amount of cobalt atom added is usually 1 to 0.00001 mol, preferably 0.1 to 0.0001 mol.

The organic phosphine compound is usually 0.1 m as a phosphorus atom for 1 mol of cobalt in the cobalt compound.
ol or more, preferably 1 to 1000 mol, more preferably 1 to 100 mol, particularly preferably 1 to 20 mol.

Further, the aluminum compound is usually 1 to 1 mol as an aluminum atom with respect to 1 mol of cobalt in the cobalt compound.
It is added in the range of 100 mol, preferably in the range of 2 to 20 mol.

The above acetylene compound is usually added in an amount of 1 to 100 mol, preferably 3 to 20 mol, per 1 mol of cobalt atom in the cobalt compound.

Furthermore, when a boron halide compound is used, it is usually 1 to 1 mol with respect to 1 mol of the cobalt atom in the cobalt compound.
It is added in an amount of 100 mol, preferably 1 to 10 mol. When a protonic acid having a pKa of 1 or less is used, it is usually added in an amount of 1 to 100 mol, preferably 1 to 10 mol, per 1 mol of cobalt atom in the cobalt compound.

As the reaction temperature, a temperature of 50 ° C. or lower is usually adopted. At a temperature higher than 50 ° C, the production ratio of the above-mentioned isomers other than the desired product, 3-methylbutene-1, increases. The reaction temperature is preferably in the range of -20 ° C to 50 ° C, more preferably -5 ° C to 45 ° C.

The reaction pressure is usually from normal pressure to 100 kg / cm ² .

The reaction is usually performed in the presence of a solvent. As a solvent,
Any solvent inert to the reaction may be used, for example, toluene,
Chlorobenzene, bromobenzene, etc. can be used.

The reaction can be carried out in a batch system, a semi-continuous system, or a continuous system. The reaction product, that is, the desired 3-methylbutene-1, its isomer, 2-methylbutane, etc., can be separated by a conventional separation method such as distillation, extraction,
It can be separated by adsorption or the like. Especially when separated by distillation, the distillation residue can be recycled as a catalyst liquid.

[Work]

According to the present invention, the presence of an acetylene compound in the reaction system can increase the 3-
Although the reason why the high selectivity of methylbutene-1 can be maintained is not always clear, it is probable that an acetylene compound is a compound having a weaker coordinating power to the catalyst than isoprene but a stronger compound than 3-methylbutene-1. It is presumed that this is because it works in a competitive manner with the above to suppress the coordination of 3-methylbutene-1 to the catalyst when the isoprene reaction rate is high.

〔Example〕

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

The abbreviations represent the following, and the reaction rate and production rate were calculated by the following formulas.

IP: isoprene 3MB1: 3-methylbutene-1 2MB1: 2-methylbutene-1 2MB2: 2-methylbutene-2 2MB: 2-methylbutane (*) Reduction products: 3MB1, 2MB1, 2MB2 and 2
MB Comparative Example-1 Cobalt (II) acetylacetonate dihydrate 59 mg (0.2 mmol) and triphenylphosphine 157 mg (0.6 mmol) were charged into a 100 ml volume flask, and the system was thoroughly replaced with nitrogen. After that, 20 ml of chlorobenzene was added. 0.42 ml (0.46 mmol) of a 14.5 wt% toluene solution of triethylaluminum in a chlorobenzene solution
Was added dropwise with stirring under ice cooling. Further, ethyl aluminum sesquichloride 18.4 wt% toluene solution 0.5
2 ml (0.34 mmol) was added dropwise, and finally isoprene was added in an amount of 0.
After 3 ml (3.0 mmol) was added and the inside of the system was replaced with hydrogen, hydrogen was introduced at normal pressure with vigorous stirring under ice cooling.
After the introduction, hydrogen absorption started and hydrogenation reaction proceeded.
When the reaction liquid was analyzed by gas chromatography when the hydrogen absorption amount was about 90% of the theoretical amount, the IP reaction rate was 90.
%, The production ratio of 3MB1 was 82%. When the hydrogenation reaction was further continued and the absorption of a hydrogen amount close to the theoretical amount was observed, the reaction liquid was analyzed again. As a result, the IP reaction rate increased to 98%, but the production ratio of 3MB1 was 0.4%. Almost disappeared, and conversely, the production ratio of 2MB2 increased to 87.9%.
The production ratio of reduction products other than 3MB1 and 2MB2 is 2M
B1 was 7.6% and 2MB was 4.1%.

Example-1 Triethylaluminum 10.0 wt% toluene solution 0.60 ml as a toluene solution of triethylaluminum
(0.46 mmol) of ethyl aluminum sesquichloride as a toluene solution of ethyl aluminum sesquichloride 10.0 wt% toluene solution 0.96 ml (0.34 mmo)
l) is used, and after addition of isoprene, 3-hexyne 0.1
The reaction was performed in the same manner as in Comparative Example 1 except that 8 ml (1.6 mmol) was added, and when the hydrogen absorption amount was about 90% of the theoretical amount, the reaction solution was analyzed.
%, The production ratio of 3MB1 was 81%. When the IP reaction rate was further increased and absorption of a hydrogen amount close to the theoretical amount was observed, the reaction solution was analyzed, and the following results were obtained.

IP reaction rate 93% 3MB1 production ratio 81% 2MB1 〃 3.6% 2MB2 〃 15% 2MB 〃 0.3% Example-2 3-trimethylhexylacetylene in place of 3-hexyne.
The reaction was carried out in the same manner as in Example 1 except that 23 ml (1.6 mmol) was used, and when the hydrogen absorption amount was about 90% of the theoretical amount, the reaction solution was analyzed.
%, The production ratio of 3MB1 was 81%. When the IP reaction rate was further increased and absorption of a hydrogen amount close to the theoretical amount was observed, the reaction solution was analyzed, and the following results were obtained.

IP reaction rate 96% 3MB1 generation rate 81% 2MB1 〃 3.6% 2MB2 〃 15% 2MB 〃 0.4% Example-3 3-phenyl acetylene 0.17 ml instead of 3-hexyne
The reaction was carried out in the same manner as in Example 1 except that (1.6 mmol) was used, and when the hydrogen absorption amount was about 90% of the theoretical amount, the reaction solution was analyzed. Three
The MB1 production ratio was 83%. When the IP reaction rate was further increased and absorption of a hydrogen amount close to the theoretical amount was observed, the reaction solution was analyzed, and the following results were obtained.

IP reaction rate 96% 3MB1 production rate 83% 2MB1 〃 3.7% 2MB2 〃 13% 2MB 〃 0.3% Example-4 3-285 phenyl diacetylene instead of hexyne
The reaction was carried out in the same manner as in Example 1 except that (1.6 mmol) was used, and when the hydrogen absorption amount was about 90% of the theoretical amount, the reaction solution was analyzed. 3M
The B1 production ratio was 81%. When the IP reaction rate was further increased and absorption of a hydrogen amount close to the theoretical amount was observed, the reaction solution was analyzed, and the following results were obtained.

IP reaction rate 93% 3MB1 production rate 81% 2MB1 〃 4.7% 2MB2 〃 14% 2MB 〃 0.3% [Effect of the invention] According to the method of the present invention, it is selectively higher than isoprene which is a cheap raw material. Since the 3-methylbutene-1 can be produced with a high yield and a sufficiently fast reaction rate, and the high selectivity of 3-methylbutene-1 can be maintained at a high isoprene reaction conversion rate, the method of the present invention is , Industrial value is extremely high.

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Claims (2)

[Claims] 1. A partial hydrogenation reaction of isoprene in the presence of a catalyst composed of a cobalt compound, an organic phosphine compound and an aluminum compound to give 3-methylbutene-1.
3-methylbutene-1 characterized in that an acetylene compound is present in the reaction system in the method for producing
Manufacturing method. 2. A partial hydrogenation reaction of isoprene in the presence of a catalyst comprising a cobalt compound, an organic phosphine compound, an aluminum compound, a boron halide compound and / or a protonic acid having a pKa of 1 or less to produce 3-methylbutene-1. A method for producing 3-methylbutene-1, which is characterized in that an acetylene compound is present in the reaction system.