JPS6089436A - Production of 1,4-diene compound - Google Patents

Abstract

PURPOSE:To produce a 1,4-diene compound with reduced amount of catalyst, by reacting ethylene with a 1,3-diene compound in the presence of a 1,4-diene compound, using a catalyst composed of a Co compound, a P compound and an organic Al compound, without using an inert solvent. CONSTITUTION:A 1,4-diene compound is produced by reacting ethylene with a 1,3-diene compound in the presence of a catalyst composed of a Co compound, a P compound and an organic Al compound. The reaction is carried out without using an inert solvent at 60-120 deg.C under 3-50kg/cm<2>G in the presence of a 1,4- diene compound at the initial stage of the reaction. The amount of the 1,4-diene compound present at the initial stage of the reaction is preferably 0.1-5mol per 1mol of the 1,3-diene compound used as a raw material. EFFECT:Since the catalyst is stabilized by the 1,4-diene compound present in the system at the initial stage of the reaction, the amount of the catalyst can be decreased and the catalyst can be used repeatedly without causing the lowering of the activity. The rate of reaction and the selectivity are high.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 1,4-dienes by reacting ethylene with 1,3-dienes. More specifically, the present invention relates to a method for producing 1,4-dienes by reacting ethylene and 1,3-dienes in the presence of 1,4-dienes at the initial stage of the reaction.

BACKGROUND OF THE INVENTION As a method for producing 1,4-dienes by reacting ethylene and 1,3-dienes using a cobalt compound, for example, Japanese Patent Publication No. 7525/1983 describes a method for producing 1,4-dienes using cobalt salts and monophosphorus. Methods using phytes and organoaluminum compounds are described. This method has the disadvantage that the ethylene pressure is as high as several tens of 9/a/l G and that the reaction time is long unless the catalyst concentration is high. Furthermore, in Japanese Patent Publication No. 45-9165, Japanese Patent Publication No. 47-41321, and Japanese Patent Publication No. 45-7284, cobalt compounds,
A method using a tertiary phosphine compound and an organoaluminum compound as a catalyst has been described, but the catalyst concentration is high, and if the catalyst is still reused, the reaction rate is significantly reduced. All of these known methods use aliphatic saturated hydrocarbons, aromatic hydrocarbons, hano-logenated saturated hydrocarbons, etc. as solvents.

Summary of the Invention The inventors of the present invention have solved the problems of these known techniques, and as a result of their studies to carry out the reaction more advantageously, the present inventors have developed a method that uses an extremely small amount of catalyst and can be repeated and reused. They have also discovered a method that causes significantly less reduction in activity, and have completed the present invention.

That is, the present invention provides a method for producing 1,4-dienes by reacting ethylene with 1,3-dienes using a catalyst consisting of a cobalt compound, a phosphorus compound, and an organoaluminum compound, in which an inert solvent is not used. Without using,
A method for producing 1,4-dienes is characterized in that the reaction is carried out in the presence of 1,4-dienes at the initial stage of the reaction.

Effects of the present invention The method of the present invention has the following advantages compared to conventional methods.

(1) A small amount of catalyst is required.

Compared to conventional methods, Ogawa's catalyst is more effective than conventional methods, as the catalyst is stable and its activity does not decrease even when used repeatedly, so there is no need to add organic aluminum.

(2) Reaction speed is faster than a dog.

(3) High selection rate.

Since it suppresses the high oligomerization of 1,3-diene, 1,
High selectivity for 4-dienes.

(4) The reaction proceeds sufficiently even if the ethylene supply pressure is low.

(5) No decomposition agent is required.

Since it is a stable catalyst with suitable activity, no decomposer is required at the end of the reaction.

(6) Eliminates the need for inert solvents.

The presence of 1,4-hexadiene at the initial stage of the reaction not only stabilizes the catalyst, but also serves as a solvent when present in an appropriate amount, so that an inert solvent is not required to facilitate the reaction.

(7) Catalyst recovery is easy.

Since a decomposer and a solvent are not used, their removal is not necessary and catalyst recovery is easy.

(8) A highly pure target product can be obtained by simple distillation.

Due to the high selectivity and the absence of use of decomposers and inert solvents, the target product 1,4-hexadiene can be obtained with high purity by simple distillation alone.

(9) Industrially advantageous.

In addition to the above-mentioned various advantages, the present invention is an industrially extremely advantageous method for producing 1,4-hexadiene, especially in mass production, since stable production can be achieved at low cost.

As mentioned above, the method of the present invention is completely different from conventional methods in which chemically inert solvents such as aliphatic saturated hydrocarbons, aromatic hydrocarbons, or halogenated saturated hydrocarbons are commonly used as solvents. The many benefits it brings are still completely unpredictable.

Specific explanation (1) 1,3-dienes The 1,3-dienes that are a component of the starting material of the present invention are linear or branched 1,3-dienes having 4 to 12 carbon atoms. Examples are 1,3-butadiene, isoprene, piperylene, 2-ethyl-1,3-phtadiene, 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene, 4
, 4-dimethyl-1,3-butadiene, 1,4-dimethyl-1,3-butadiene, ■, 3-octadiene, 1,
Examples include 3-decadiene and 1,3-dodecadiene.

(2) Catalyst The catalyst used in the method of the present invention is a cobalt compound, a phosphorus compound, an organoaluminium compound, etc., which were conventionally used when reacting ethyleneto-1,3-dienes to produce l,4-dienes. If the slurping percentage is 9%,
Either can be used.

That is, catalysts used in Japanese Patent Publication No. 45-7525, Japanese Patent Publication No. 9165-1982, Japanese Patent Publication No. 41321-1977, Japanese Patent Publication No. 45-7284, etc., which are already mentioned as known techniques, can be used.

Cobalt compounds include halides, inorganic salts, aliphatic or aromatic carboxylates having 1 to 12 carbon atoms, aliphatic or aromatic β-diketones having 3 to 12 carbon atoms, or aliphatic or aromatic β-diketones having 4 to 15 carbon atoms. A cobalt-coordination inclusion of an aliphatic or aromatic β-ketocarboxylic acid is used. Specifically, for example, cobalt chloride, cobalt fluoride, cobalt bromide, cobalt iodide, cobalt nitrate, cobalt sulfate, cobalt carbonate, cobalt thiocyanate, cobalt formate, cobalt acetate, cobalt propionate, cobalt acrylate,
Conolt adipic acid, cobalt vinyl acetylate, cobalt octenoate, cobalt cresylate, cobalt benzoate, cobalt naphthenate, cobalt hexanedionate , 1-phenylbutanedionatocobalt, 1
-phenylpentanedionatocobalt), 1,3-diphenylpropanedionatocobalt, 1,5-diphenylpentanedionatocobalt, cobalt acetyl acetate, cobalt acetoacetate, propionyl cobalt acetate, butanoyl cobalt acetate, hexanoyl cobalt acetate, hendyl acetate Examples include cobalt.

As the phosphorus compound, a phosphite compound (I), a diphosphine compound (U), and a diphosphine oxide compound (I[D) represented by the following general formula are used.

(R”0)aP (I) (R2)2P (R3)m P(R2)2 (1)('
R2)2P (R3)m P(R2)2 (I[I) In the formula, R1 is an alkyl group having 1 to 10 carbon atoms, 6 to 10 carbon atoms which may be substituted with halogen or phenyl group, etc.
represents an aryl group. R1' represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 1 to 12 carbon atoms; R3 is an alkylene group having 1 to 10 carbon atoms;
Represents a phenylene group and an alkenylene group having 2 to 10 carbon atoms. m is 0 or 1.

Examples of phosphite compounds include triethyl phosphite, tributyl phosphite, triphenyl phosphite, tri0-tolylphosphite, trirn-
) lylphosphite, tri-p-) IJ lylphosphite, tri-p-chlorphenylphosphite, tri-m-chlorphenylphosphite tri-p-bromphenylphosphite, tri-2,4-dichlorophenylphosphite),) IJ- Examples include p-biphenylylphosphite. Diphosphine compounds include bisdimethylphosphine, bisdiethylphosphine, bisdibutylphosphine, bisdiethylphosphine, bisdioctylphosphine, bisdidodecylphosphine, bisdiphenylphosphine, bisditrylphosphine, bisdimethylphosphine, bisdiethylphosphinomethane, Bisdiethylphosphinomethane, bisdiphenylphosphinomethane, bis(1,2-dimethylphosphino)ethane, bis(1,2-diethylphosphino)ethane, bis(
1,2-dipropylphosphino)ethane, bis(1,2
-dibutylphosphino)ethane, bis(1゜2-dihexylphosphino)ethane, bis(1,2-dioctylphosphino)ethane, bis(1,2-diphenylphosphino)ethane, bis(1,2-dibutylphosphino)ethane, tolylphosphine)ethane, bis(1,2-dinaphthylphosphino)ethane, bis(1,3-diethylphosphino)propane, bis(1
,3-dibutylphosphino)propane, bis(1,3-
dihexylphosphino)propane, bis(1,3-diphenylphosphino)propane, bis(1,4-diphenylphosphino)butane, tetramethyldiphosphine, tetraethyldiphosphine, bis('',2-dimethylphosphino)benzene, bis (1,2-diethylphosphino)benzene, bis(1,2-dibutylphosphino)benzene, bis(1,2-dihexylphosphino)benzene, bis(1,2-dioctylphosphino)benzene, bis(1,2-dibutylphosphino)benzene, ,2-diphenylphosphino)benzene, bis(
1,2-ditolylphosphine)benzene, bis(2,3
-diethylphosphino)naphthalene, bis(2,3-dibutylphosphino)naphthalene, bis(2,3-diphenylphosphino)naphthalene, bis(1,2-dimethylphosphino)ethylene, bis(1,2-diethyl) phosphino)ethylene, bis(1,2-dibutylphosphino)
Ethylene, bis(1,2-cy'<antylphosphino)
Examples include ethylene, bis(1,2-dioctylphosphine)ethylene, bis(1,2-diphenylphosphino)ethylene, and bis(1,2-ditolylphosphino)ethylene. Examples of the diphosphine oxide compound include oxide compounds corresponding to the specific examples of the diphosphine compound described above. Among these, diphosphine compounds are preferred.

As the organic aluminum compound, a compound represented by the following formula is used.

At(R)3-nXn In the formula, R is an alkyl group having 1 to 12 carbon atoms, and 3 to 1 carbon atoms.
0 represents a cycloalkyl group, X represents hydrogen or halogen, and n represents Oll, 1.5.2. However, X
When is hydrogen, n is 1.

Examples of the aluminum compound include trimethylaluminum, triethylaluminum, tri-H-propylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum,
Tridecylaluminum, diisobutyl-n-hexylaluminum, diethylaluminum hydride, diisopropylaluminum hydride, diisobutylaluminum hydride, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminium bromide, dipropylaluminum chloride, diisobutylaluminum chloride, diptylaluminium bromide ,
Diethylaluminum iodite, diptylaluminum chloride, diimbutylaluminum chloride, diimbutylaluminum bromide, diimbutylaluminum 70 lide, diakylaluminum chloride, dioctylaluminum chloride, didodecylaluminum chloride, diphenylaluminum chloride, ditolylaluminum chloride, Dibenzylaluminium bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, propylaluminum sesquichloride, isobutylaluminum sesquipromide, hexylaluminum sesquichloride, octylaluminum sesquipromide, phenylaluminum sesquichloride, trialaluminum sesquichloride, benzylaluminum sesquichloride, ethylaluminum dichloride,
Examples include methylaluminum diiodite. Among these aluminum compounds, those with n of 1,1.5 or 2 are preferable, particularly those with n of 1 and those with n of 1.5 or 2.
It is preferable to use it in combination with Further, R is preferably an alkyl group.

Specifically, combinations of dialkylaluminum chloride and alkylaluminum sesquichloride, or combinations of trialkylaluminum and dialkylaluminum hydride are particularly preferred.

(311,4-!l) Dienes The 1,4-dienes present in this reaction stably maintain appropriate catalytic activity by coordinating with or leaving cobalt, which is the central metal of the catalyst. , suppresses the formation of high oligomer compounds of 1,3-diene, and efficiently converts ethylene and 1.
React 1 mole each of 3-dienes to obtain the desired 1.4-
It is thought to have the same function as dienes. child\
Functionally, various 1.4-dienes can be used as the 1.4-dienes used in the above, but from the viewpoint of reaction operation, post-treatment, etc. It is reasonable to use dienes. These 1,4-dienes are linear or branched 1,4-dienes having 6 to 14 carbon atoms.
-Dienes, such as 1,4-hexadiene, 4-
and 5-methyl-1,4-hexadiene, 1,4-hebutadiene, 4- and 5-ethyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 1.
Examples include 4-octadiene, 6-methyl-1,4-heptadiene, 1,4-dodecadiene/1°4-tetradecadiene, and the like.

(4) Usage amount and reaction conditions In the method of the present invention, ethylene and 1,3-dienes react in equivalent amounts, but these two components do not necessarily have to be present in the reaction system in an equivalent relationship; It is preferable to use 1 to 10 moles of 1,3-dienes per mole.

There is no particular restriction on the amount of the catalyst used, but the amount of cobalt compound is usually o, 000005 per mole of 1,3-dienes.
~0.1 mol, preferably 0.00001 to 0.01 mol is used. The phosphorus compound is used in an amount of 0.05 to 10 mol, preferably 2 to 3 mol, with tL<uo, per 1 mol of the cobalt compound. The amount of organoaluminum compound used is 3 to 200 mol, preferably 5 to 200 mol, per 1 mol of cobalt compound.
It is 50 moles.

1. The amount of 4-dienes to be used is determined by considering the contribution to the catalyst and the function as a solvent such as removing reaction heat.
, 3-dienes, the amount may be 0.01 mol or more, but considering practicality, it is 0.01 to 10 mol, preferably o, i to 5 mol.

The reaction temperature of the method of the present invention is 0 to 150°C, preferably 60°C.
~120°C. The reaction pressure may be normal pressure, but 2 to 100 Kq/cdG, especially 3 to 50 Kq/cdG under ethylene pressure.
dG is preferred.

In the method of the present invention, the catalyst is a cobalt metal containing a phosphorus compound and 1
．． It is thought that appropriate catalytic activity is exhibited due to the reduction by the aluminum compound after coordination of the 4-dienes. That is, it is necessary that the cobalt compound, the phosphorus compound, and the 1,4-dienes always exist simultaneously in the reaction system.

Therefore, when carrying out the present invention, the starting materials and catalyst may be charged in any order as long as they are at room temperature or below where they are inactive, but if they are charged at room temperature or above where they are immediately activated. To get good results, the order of preparation is important. That is, cobalt compounds,
After the phosphorus compound and 1,4-dienes are allowed to coexist, the aluminum compound, ethylene, or 1,3-dienes may be charged in an appropriate order.

Next, the present invention will be explained in detail using examples.

Example 1 (1) First reaction Autoclave with electromagnetic induction stirrer (inner volume 500 m1
) was replaced with nitrogen, and anhydrous cobalt chloride (0,0260f, 0.2 rnmol) bis(1
,2-diphenylphosphino)ethane (0.07979
, o, 2 m rnoL ), dehydrated and degassed methyl-1
, 4-hexadiene (150 ml), isogren (10
0ml, 1mot), triethylaluminum (0,3
01rril, 2.2 mmot), diethylaluminum chloride (0,803 mA!, 6.4 mmoA
) and sealed. The temperature was raised to 90 ci, the pressure was increased to 9 K9/cdI Q with ethylene, the mixture was allowed to react for 30 minutes, and then cooled. Next, the reaction solution was taken out into a 500 ml flask that was purged with nitrogen so as not to be exposed to air.

As a result of gas chromatography analysis of the contents,
The conversion rate of isopre is almost 100%.
．． The in-plane yield of 4-hexadiene was 92%.
Simple distillation. The resulting pot residue containing the catalyst was charged into an autoclave in the same manner as in (]), and then methyl-hexadiene 1501d and isoprene (100 ml, 1 mo
t) was charged, and the reaction was carried out in the same manner as described above. As a result, the reaction was completed in 40 minutes, and the yield of methyl-1,4-hexadiene versus the charged isoprene was 91%.

(3) Third reaction The catalyst was recovered a second time in the same manner as in (2), and the reaction was completed in 90 minutes, with a yield of 91% of the isoprene charged.

Example 2 Isoprene in Example 1 was replaced with fridien (54r, 1
rnot) and 1.4 methyl-1,4-hexadiene.
The reaction, analysis, and catalyst recovery were carried out in the same manner, except that bis(1,2-diphenylphosphino)ethane was replaced with bis(1,2-diethylphosphino)benzene. As a result, the first reaction was completed in 25 minutes, the conversion rate of butadiene was yiooo%, and the yield of butadiene based on the amount of butadiene charged was 87%.

The second reaction was completed in 40 minutes, and the yield of 1,4-hexadiene versus butadiene charged was 88%.

The third reaction was completed in 85 minutes, and the yield of 1,4-hexadiene versus butadiene charged was 89%.

Example 3 In Example 1, the amounts of each reagent were changed to anhydrous cobalt chloride (0,00390f, 0.03 m rnoA ), bis(1,2-diphenylphosphino)ethane (0,01
202,0,03 mmol), triethylaluminum (0,0451 ml, 0.330 mmot), diethylaluminum chloride (0,120 me, 0.96
The reaction and analysis were carried out in the same manner except that 0rn mot) was used.

As a result, the reaction was completed in 50 minutes, the conversion of imprene was 99%, and the yield of methyl-1,4-hexadiene based on the amount of isoprene charged was 90%.

Comparative Example 1 Reaction and analysis were carried out under the same conditions as in Example 1 except that methyl-1,4-hexadiene was replaced with toluene.

As a result, the -th reaction time was 90 minutes, which was a slow reaction rate. The conversion rate of isoprene was approximately 100%, and the yield of isoprene from methyl-1,4-hexadiene was 91%.

The second reaction is extremely slow, so Triech A/7
A/minium (0,151ml, 1.1 mmo, a
) and diethylaluminum chloride (0,402m
l.

The catalyst was activated by adding 3.2 m mot), but the reaction time was as long as 270 minutes.

Comparative Example 2 The reaction and analysis were carried out under the same conditions as in Example 1 except that heptane was used instead of methyl-1,4-hexadiene.

As a result, the first reaction time was 80 minutes, and the reaction rate was slow. The conversion rate of isoprene is approximately io.

%, and the yield of methyl-1,4-hexadiene versus charged isoprene was 90%.

In the second reaction, triethylaluminum (0,+51
ml, 1.1 mmoA) and diethylaluminum chloride (0,402 ml, 3.2 m mat )
was added to activate the catalyst, but the reaction time was 30
It was 0 minutes long.

Comparative Example 3 In Example 3, the solvent was changed from methyl-1,4-hexadiene to toluene, and the amount of catalyst was three times or more, that is, anhydrous cobalt chloride (0,0130f, 0.'1 mmot), bis(1,2 -diphenylphosphino)ethane (0,03
99? , 0.1 mmot),) ethylaluminum (
0,151 mJ, 1.1 mmot), diethylaluminium chloride (0,402 mJ, 3.2 m mob)
As a result, the reaction time was as long as 300 minutes.

Same as Masahisa Hase

Claims (1)

[Claims] A method for producing 1,4-dienes by reacting ethylene with 1,3-dienes using a catalyst consisting of a cobalt compound, a phosphorus compound, and an organoaluminium compound, without using an inert solvent, A method for producing 1,4-dienes, characterized in that the reaction is carried out in the presence of 1,4-dienes at the beginning of the reaction.