JP3525461B2 - Method for dimerizing butene and method for producing alcohol using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for dimerizing butene (hereinafter sometimes referred to as butenes) using a specific catalyst, and octene (hereinafter referred to as octenes) produced by a dimerization reaction of butenes. The present invention relates to a method for producing an alcohol useful as a plasticizer raw material, using a dimerization composition of butenes mainly containing

[0002]

2. Description of the Related Art A catalyst system for homogeneously dimerizing a lower monoolefin such as ethylene, propylene and butene has been extensively studied so far. As the catalyst, a Ziegler type catalyst having a transition metal as a central catalyst component is usually excellent in terms of dimer selectivity of a lower monoolefin, and in particular, a catalyst obtained from a mixture of a nickel compound and an organic aluminum halide. In the case of using, the dimerization activity and the selectivity are good. Further, regarding the dimerization of butenes, as a method for giving an improved octene yield, Japanese Patent Publication No.
From a nickel compound selected from the group consisting of nickel salts of higher mono- or di-carboxylic acids having 5 to 20 carbon atoms and a coordination complex of an organic phosphine and a nickel halide, an organoaluminum compound and hydrogen. The following catalyst systems have been proposed.

In the dimerization reaction of these butenes, the octenes formed are not only a mixture of various skeletal isomers, for example, n-octene, 3-methylheptene, 3,4-dimethylhexene and the like skeleton isomers. It is generally known that a mixture of a large number of double bond isomers can be obtained by an isomerization reaction that competitively occurs with a dimerization reaction. Further, an alcohol having 9 carbon atoms obtained by subjecting the octenes obtained by the above dimerization reaction to a hydroformylation reaction and a hydrogen reaction (hereinafter, referred to as “INA”)
It is already known that is preferably used as a raw material of a plasticizer for vinyl chloride resin (US Pat. No. 789,777).
No. 61-15849). And INA is
Compared to 2-ethylhexanol obtained by hydroformylation, dimerization and hydrogenation of propylene, which has been widely and widely used as an alcohol for a plasticizer raw material, it is superior in heat resistance and low-temperature flexibility. It is also known to be an alcohol for plasticizers of vinyl chloride resins.

On the other hand, other than the dimerization method of butenes, there is an oligomerization reaction of olefins as a method for producing octenes. For example, JP-A-1-132534 discloses that
A method for oligomerizing an olefin having 2 to 10 carbon atoms by using a zeolite catalyst whose surface is treated with a trialkylpyridine compound or an organic phosphorus compound is disclosed.

[0005]

As described above, octenes obtained by dimerization of butenes have a linear structure as well as various branched chain structures and have a large number of different double bond positions. Obtained as a mixture of isomers. When these products are used, for example, as a raw material for the above-mentioned hydroformylation reaction, generally, the lower the degree of branching is, the higher the hydroformylation reaction activity is, and the octenes having a high degree of branching remain in the system as unreacted substances. . In addition, when INA produced by the hydroformation and hydrogenation reaction of octenes is used as a plasticizer raw material, INA with a lower degree of branching is a more important performance of vinyl chloride resin, such as cold resistance and volatility. Has the advantage of being excellent.

However, in the dimerization reaction of butenes, the reaction substrate generally contains a large amount of an internal olefin such as 2-butene, and the reaction substrate containing a large amount of such an internal olefin is economical and highly efficient. It is extremely difficult to obtain octenes with a high yield and a low degree of branching. Even in the dimerization catalyst system of n-butenes proposed in the above Japanese Patent Publication No. 3-42249, the resulting octene mixture has a high production rate of 3,4-dimethylhexene with a high degree of branching, and thus is industrially used. In particular, it is not very suitable for use in the plasticizer field mentioned above. Also, the above-mentioned US Patent No. 78977.
I proposed in No. 7 and Japanese Patent Publication No. 61-15849
The NA manufacturing method is not always satisfactory in this respect.

Further, even in the method for oligomerizing olefins proposed in JP-A-1-132534, since the product is obtained as an olefin mixture having a wide range of carbon numbers, the fractionation step is complicated, and Considering that the octene selectivity in the product is not always sufficient, etc., it is not always satisfactory as a method for economically and selectively producing octenes. Therefore, in the dimerization of butenes, the development of a catalyst system capable of improving the yield of octenes and the selectivity of octenes with low branching degree, and the selective and high yielding of INA with low branching degree. It is a problem to be solved by the present invention to develop a manufacturing method.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems in the production of octenes and INA, and as a result, the butenes were converted into dibutenes using a specific dimerization catalyst. If it is quantified, it is possible to selectively produce octenes in a high yield and in a specific range, and if INA is produced using the octenes in the specific range, the plasticizer performance is remarkably improved. The present invention has been completed by finding out the above.

That is, the butene dimerization method of the present invention is a method of dimerizing butene containing 2-butene in the presence of a catalyst, wherein (i) it has no nickel-halogen bond and has 1 to 10 carbon atoms. Using an organonickel compound which is a carboxylate salt of 18, (ii) a triarylphosphine and / or a monoalkyldiarylphosphine, (iii) an alkylaluminum halide compound and (iv) a catalyst system generated in situ from hydrogen It is characterized by doing. Furthermore, the method for producing an alcohol of the present invention is characterized in that the octene obtained by the dimerization method is subjected to a hydroformylation reaction and a hydrogenation reaction.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. Examples of butenes used in the present invention include 1-butene and 2-butene, each of which is a single product, or a mixture thereof.
Or C obtained by thermal decomposition of hydrocarbon oil such as naphtha
A butene fraction having a high n-butene content after separating butadiene and isobutene from the 4 fraction (BB fraction) can be preferably used. Further, the BB fraction obtained by catalytic cracking of hydrocarbon oil such as heavy oil (FCC, etc.) is mainly a mixture of butene and butane, and has a high n-butene content after isobutene is separated by distillation. Butene fraction and the like can also be preferably used.

For the dimerization reaction of these butenes,
By using the specific catalyst system used in the present invention, octenes having extremely low branching degree can be produced with high activity. Here, the branching degree represents the number of groups such as a methyl group and an ethyl group branched from the hydrocarbon main chain, and for example, n-
The branching degrees of octene, 3-methylheptene and 3,4-dimethylhexene are 0, 1 and 2, respectively. The average degree of branching of octenes is the average value of the degree of branching of octene components (n-octene, 3-methylheptene, 3,4-dimethylhexene, etc.) in the octene mixture. For example, 3-
The average degree of branching in the case of a mixed octene containing equal amounts of methylheptene and 3,4-dimethylhexene is 1.5.

The dimerization reaction catalyst used in the present invention has (i) no nickel-halogen bond, and a carbon number of 1 to 1
An organonickel compound which is a carboxylate salt of 18, (ii)
Triarylphosphine and / or monoalkyl
A catalyst system generated in situ from a diarylphosphine, (iii) an alkylaluminum halide compound and (iv) hydrogen.

Examples of the organic nickel compound which is a carboxylic acid salt having 1 to 18 carbon atoms and having no nickel-halogen bond used in the present invention include various organic nickel salts, specifically, nickel formate. , Nickel trifluoroacetate, nickel oxalate, nickel acetate, nickel octoate, nickel dodecanoate, nickel naphthenate,
Examples thereof include nickel carboxylates such as nickel oleate and nickel benzoate. These carboxylic acid salts are preferably used after dehydration, and more preferably a carboxylic acid salt having 1 to 8 carbon atoms, further preferably a carboxylic acid salt having 1 to 4 carbon atoms. Other preferable examples include bis (acetylacetonato) nickel, bis (hexafluoroacetylacetonato) nickel,
Examples thereof include complex compounds containing no inorganic root such as bis (cyclooctadiene) nickel, and acetylacetonate complex compounds are particularly preferable.

When a nickel-phosphine complex compound in which a halogen is directly bonded to nickel is used as the organonickel compound, the dimerization activity may be lowered or the selectivity of desired octenes may be lowered. is there. Specifically, the organic nickel salt is NiCl ₂ (PEt ₃ ) ₂ or NiCl ₂ (PCy ₃ ) ₂ (Et is an ethyl group, C
y represents a cyclohexyl group), the octenes formed have a highly branched product distribution, although the dimerization reactivity proceeds favorably when the coordination phosphine is an alkyl or cycloalkylphosphine. On the other hand, when the halogenated organonickel complex compound coordinated with the arylphosphine used in the present invention such as NiCl ₂ (PPh ₃ ) ₂ (where Ph represents a phenyl group) is used, the octene produced is The classes show a product distribution with a low degree of branching, as in the case of the catalyst system of the invention, but with lower dimerization activity.

The reason for the low activity in this case is the low solubility of the nickel complex, and the nickel halide complex coordinated with a triarylphosphine (soft phosphine) such as PPh ₃ described above is PEt _3. And PCy ₃
As compared with a nickel halide complex in which a trialkylphosphine (hard phosphine) is coordinated, or a combination of a nickel compound in which halogen is not directly bonded to nickel and a phosphine,
In general, the solubility of the solvent and butenes, which is a reaction substrate, is low, and it is presumed that the reactivity is reduced because the amount of the active catalyst component contributing to the dimerization reaction is reduced.

The following compounds can be used as the alkylaluminum halide compound. That is,
Monohalogeno / dialkylaluminums and dihalogenomonomonomers represented by the general formulas AlR ₂ X, AlRX ₂ , Al ₂ R ₃ X ₃ (wherein R represents an alkyl group having 1 to 5 carbon atoms, and X represents a halogen atom). Examples of the alkylaluminum or sesquihalogeno-alkylaluminum compound include diethylaluminum monochloride, ethylaluminum dichloride, ethylaluminum sesquichloride, propylaluminum dichloride, isobutylaluminum dichloride and the like. Of these, dihalogenomonoalkylaluminum compounds such as ethylaluminum dichloride are more preferable.

In the process of the present invention, by using an organonickel compound having no nickel-halogen bond, an alkylaluminum halide compound and hydrogen and a catalyst system formed in situ from a triarylphosphine or monoalkyldiarylphosphine. It is possible to obtain an octene mixture with a high yield and a low branching degree, and by using this as a raw material, the reaction activity of hydroformylation is increased, and a mixed alcohol (INA) obtained through hydroformylation and hydrogenation reaction is obtained. It is possible to reduce the branching degree of.

When the catalyst component does not contain the phosphine compound used in the present invention, or when another phosphine compound such as trialkylphosphine or tricyclohexylphosphine is used, the degree of branching of the obtained octenes is satisfactory. However, the plasticizer performance of INA produced from these octenes as a raw material is not always satisfactory. The performance of the plasticizer depends on the plasticization efficiency,
It is necessary to comprehensively evaluate volatilization loss (heat resistance), low temperature flexibility, kerosene extractability (oil resistance), electrical resistance (insulation property), etc., and it is not only a single property such as heat resistance. However, the INA obtained by the method of the present invention gives excellent plasticizer performance as a whole.

Examples of the triarylphosphine used in the present invention include the general formula PAr _{3 (} where Ar represents a phenyl group or a naphthyl group which may have a substituent, and the substituent has 1 to 1 carbon atoms). 6 alkyl groups, aryl groups, hydrocarbon groups such as cycloalkyl groups, alkoxy groups,
Alternatively, a compound represented by a halogen atom such as Cl, Br, or F) can be used. Specifically, triphenylphosphine, tris (p-chlorophenyl) phosphine, tris (p-fluorophenyl) phosphine, tris (m
-Chlorophenyl) phosphine, tris (p-methoxyphenyl) phosphine, tris (o-methoxyphenyl) phosphine, tris (p-biphenylyl) phosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri-o-tolyl Phosphine, Tris (p-
Isopropylphenyl) phosphine, tris (2,4,
6-trimethylphenyl) phosphine, tris (3,5)
-Dimethylphenyl) phosphine, tri-1-naphthylphosphine, p-tolyl diphenylphosphine, m-
Tolyl diphenylphosphine, di-p-tolyl phenylphosphine, o-tolyl diphenylphosphine,
Examples thereof include 2-biphenylyldiphenylphosphine, 1-naphthyldiphenylphosphine, 2-naphthyldiphenylphosphine, and among these, triphenylphosphine and tris (p-substituted phenyl) phosphine are preferably used.

Further, the monoalkyl
Examples of the diarylphosphine include general formula PRA
r ₂ (wherein Ar represents a phenyl group which may have a substituent or a naphthyl group, preferably a phenyl group, and the substituent is, for example, an alkyl group having 1 to 6 carbon atoms, an aryl group or a cycloalkyl group. Etc. represents a hydrocarbon group, an alkoxy group or a halogen atom such as Cl, Br, F, etc., preferably an alkyl group having 1 to 6 carbon atoms, and R represents an alkyl group having 1 to 8 carbon atoms). Compounds can be used. Specifically, n-propyl diphenylphosphine, i-
Examples include propyl diphenylphosphine, n-butyl diphenylphosphine, n-octyl diphenylphosphine, di-p-tolyl n-butylphosphine and the like.

In the method of the present invention, hydrogen is used as the fourth catalyst component. Although its action is not clear, various factors such as removal of impurities in the reaction system (eg, reaction inhibitors such as conjugated dienes), promotion of generation of catalytically active species, contribution of catalyst stability, etc. are presumed. By doing so, the dimerization reaction activity obviously increases. The amount used is not particularly limited and may be an amount that gives a preferable result for the catalytic activity, and is usually 0.01 to 50 k as a hydrogen partial pressure.
g / cm ² , preferably 0.1 to 20 kg / cm ² .

In the dimerization reaction of butenes carried out in the present invention, an organonickel compound having no nickel-halogen bond, a triarylphosphine and / or a monoalkyl / diarylphosphine as described above, is formed in order to form the catalyst system. The compound, the alkylaluminum halide compound, and the hydrogen catalyst components may be mixed in any order. First, the organonickel compound having no nickel-halogen bond and the triarylphosphine or monoalkyl / diarylphosphine compound are mixed. It is preferable to use them after mixing them, or to use them as a complex thereof. Further, it is preferable to bring these Ni-P compounds and alkylaluminum halide compounds into contact with each other in the presence of butenes at a high yield and a low branching degree of octenes. To obtain.

In the method of the present invention, the use of a reaction solvent is not essential, but a solvent inert to the reaction, such as aromatic hydrocarbons such as benzene, toluene, xylene and dodecylbenzene, hexane, heptane, cyclohexane, etc. Aliphatic hydrocarbons and halogenated aromatic hydrocarbons such as chlorobenzene can be used in the presence thereof. The concentration of the nickel component in the liquid phase in the dimerization reaction is usually 10
^-2 to 10 ² mmol / l. The molar ratio between each catalyst component affects dimerization activity and product distribution,
The molar ratio of the organoaluminum compound to the nickel compound in the catalyst of the present invention is usually in the range of 2 to 100, preferably 5 to 50. The molar ratio of the above-mentioned triarylphosphine or monoalkyl / diarylphosphine compound to the organonickel compound is 0.0
It is 5 to 20, preferably 0.5 to 5.

If the molar ratio of the alkylaluminum halide compound to the organonickel compound in the catalyst is too low, it reacts with a small amount of oxygen or water present during the dimerization reaction to drastically reduce the catalytic activity. Even under the above high conditions, the dimerization activity is not significantly improved, and it is not economically advantageous. Further, if the molar ratio of the phosphine compound to the organic nickel compound is too low, the dimerization activity is lowered and the degree of branching of the produced octene is increased. On the other hand, if it is too high, the dimerization activity is lowered, and it is not economically advantageous, though it depends on the amount of the alkylaluminum halide compound present.

As the dimerization reaction conditions to be carried out in the present invention, the reaction temperature is usually -10 to 100 ° C, preferably 0 to
The temperature is 80 ° C., more preferably 10 to 80 ° C., but it is appropriately set depending on the productivity of the process and the stability of the organic nickel compound and the alkylaluminum halide compound used. It is effective that the catalyst component is sufficiently present in the liquid phase of butenes, and the reaction pressure is 2 to 30.
It is preferably about kg / cm ² . Further, the dimerization method of the present invention can be carried out even if the reaction raw material contains paraffin hydrocarbons such as methane, ethane, propane and butane, and inert gases such as nitrogen, argon and carbon dioxide. . The dimerization reaction system may be a continuous system or a batch system.

In the dimerization method of the present invention, the reaction conditions, particularly the catalyst concentration, the reaction temperature, and the reaction time (contact time) have a great influence on the product selectivity. Generally, the reaction activity is improved by increasing the reaction conditions, but the selectivity of the desired octenes is decreased because the reactivity of trimerization or higher is also increased,
In particular, the content of normal body and monomethyl body is reduced.

By the dimerization reaction carried out in the present invention,
Particularly, it is possible to selectively obtain high-yield octenes as a raw material of INA for a plasticizer in a high yield. In particular, the octenes produced in the present invention are usually solid phosphoric acid catalysts or Si
Almost no skeleton isomer with carbon-carbon bond cleavage, which is generated when a dimerization reaction is carried out with a catalyst in which Ni is supported on an inorganic porous carrier such as O ₂ or Al ₂ O ₃ , is contained, and normal octene is contained. The total content of monomethylheptene and dimethylhexene is 90% by weight or more. In addition, the content of the highly branched compound of 2-branched dimethylhexene or higher is 15% by weight or less, and the above-mentioned octenes have an average degree of branching of 1.15 or less. Furthermore, the content of octenes in the product obtained by the dimerization reaction is 7
It is 0% by weight or more. Here, the high molecular weight product means that the molecular weight that is generally generated in the oligomerization reaction of butenes is 4
A compound of 00 or less is meant.

Such octenes having a low degree of branching have a higher conversion than conventional octene compositions even when used in a method for producing an aldehyde which is a precursor of an alcohol for a plasticizer, that is, a hydroformylation reaction. The reaction can be pushed up to the limit, and it is a preferable compound from the economical point of view. Further, when the octenes are led to an alcohol through a hydroformylation reaction and a hydrogenation reaction, a plasticizer produced from the octenes has a cold resistance which is a plasticizer performance as compared with a plasticizer derived from a conventional octene composition, Since the properties such as brittleness and volatility are improved, it has great utility value industrially.

As a dimerization composition of butenes mainly composed of octenes which gives the above preferable results, the content of octenes in the high molecular weight product obtained by the dimerization reaction is 70% by weight or more, It is preferably 80% by weight or more, more preferably 90% by weight or more, and the total octenes in the skeletal structure of normal octene, monomethylheptene and dimethylhexene are 90% by weight or more, preferably 95% by weight or more, Preferably 9
The content is 9% by weight or more, in which the content of highly branched dimethylhexene or more is 15% by weight or less, preferably 10% by weight or less, more preferably 7% by weight or less, further preferably 5% by weight. And the average degree of branching of the produced octenes defined below is 0.85 to 1.
15, preferably 0.85 to 1.10, more preferably 0.85 to 1.00, still more preferably 0.90 to 0.9.
It is 5.

Next, a method for producing an alcohol having 9 carbon atoms from the octene obtained by the above-mentioned dimerization reaction of butenes as a raw material will be described in detail. In the method of the present invention, usually, first, the octenes obtained by the dimerization reaction of butenes are purified by distillation under normal pressure or reduced pressure to separate high-boiling components contained in a small amount, and then purified by distillation. The octene fraction thus obtained is hydroformylated with carbon monoxide and hydrogen to produce an aldehyde having 9 carbon atoms.
The hydroformylation reaction is carried out according to a conventional method. The reaction conditions of hydroformyl are not particularly critical either, and any conventionally known rhodium method or cobalt method can be used.

In the case of the rhodium method, R is used as the rhodium source.
Organic salts such as h (OAc) ₃ , Rh (NO ₃ ) ₃ and Rh
Inorganic salt such as Cl ₃ or Rh (acac) (CO)
₂ , [Rh (OAc) (COD)] ₂ , Rh ₄ (CO)
₁₂ , Rh ₆ (CO) ₁₆ , RhH (CO) (Ph ₃ P)
₃ , [Rh (OAc) (CO) ₂ ] ₂ , [RhCl (C
OD)] ₂ and other complexes can be used. (Here, Ac represents an acetyl group, acac represents acetylacetonate, and COD represents cyclooctadiene.)

As the cobalt source in the case of the cobalt method,
Organic acid salts such as cobalt laurate, Co (NO ₃ ) ₂
In addition to inorganic acid salts such as Co ₂ (CO) ₈ , CoH (C
O) ₄ and other complexes can be used. The reaction stress is usually normal pressure to 300 kg / cm ² G, the reaction temperature is usually 50 ° C. to 150 ° C., the H ₂ / CO ratio is usually 1 to 10 in molar ratio, and the catalyst concentration is usually 0.1-10
The condition of 00 ppm (as Rh atom) is adopted. As the ligand, an organic phosphorus compound such as triphenylphosphine or triphenylphosphite or an oxide thereof is usually used in a molar ratio of 1 to 1000 with respect to the catalyst.

A reaction solvent may not be used, but if necessary, a solvent inert to the reaction, such as benzene or toluene,
Aromatic hydrocarbons such as xylene and dodecylbenzene, aliphatic hydrocarbons such as hexane, heptane and cyclohexane,
Ethers such as dibutyl ether, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetrahydrofuran, and esters such as diethyl phthalate and dioctyl phthalate are used.
Further, aldehydes and alcohols produced by the hydroformylation reaction can be used as the solvent. Further, a high boiling point by-product such as an aldehyde polycondensate can also be used. The reaction system may be either a continuous system or a batch system.

In the above-mentioned hydroformylation reaction, not only the effect of the ligand but also the structure of the aldehyde produced varies greatly depending on the central metal catalyst used. That is, in general, a rhodium catalyst has an extremely high hydroformylation activity as compared with a cobalt catalyst, but a branched chain aldehyde is easily generated due to its strong internal isomerization ability. However, since the octenes used in the present invention described above have a low degree of branching, the alcohol finally obtained can have a relatively low degree of branching even when the hydroformylation reaction of the rhodium method is carried out, and the hydroformylation is carried out. There is an advantage that the activity is also increased.

Next, an alcohol having 9 carbon atoms is produced by a hydrogenation reaction of the obtained aldehyde, which can be carried out by a usual method. That is, an ordinary hydrogenation catalyst such as Ni, Cr, or Cu is used, and the reaction stress is usually from atmospheric pressure to
150 kg / cm ² G, reaction temperature is usually 40 ° C to 30
It is carried out at 0 ° C. Next, the number of carbon atoms is reduced to 9 by ordinary distillation purification.
Alcohol (ie, INA) can be obtained. The INA obtained as described above is subjected to an esterification reaction with an acid such as phthalic anhydride or adipic acid by a usual method, and then purified to obtain a plasticizer (eg, phthalate plasticizer).
And the resulting plasticizer has excellent performance.

[0036]

EXAMPLES Specific embodiments of the present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by the following examples without departing from the gist thereof.

Examples 1-5 and Comparative Examples 1-8 0.024 mmol of nickel compounds and 0.072 m of phosphine compounds shown in Table 1 in a stainless steel micro-autoclave having an internal volume of 70 ml which was degassed and then replaced with nitrogen.
mol and m-xylene 3 ml were charged, and then a heptane solution containing 0.3 mmol of dichloroethylaluminum was charged under a nitrogen atmosphere. However, in Comparative Example 5, Comparative Example 6 and Comparative Example 7, instead of the nickel compound and the phosphine compound, NiCl ₂ (PPh ₃ ) ₂ complex, NiCl ₂ (PEt ₃ ) ₂ complex and NiCl ₂ (P
Cy _{3) 2} complex was used 0.024mmol.

Next, after 20 ml of trans-2-butene was charged, hydrogen gas was introduced until the total pressure became 5 kg / cm ² · G, the microautoclave was sealed, and the reaction was carried out at 40 ° C. for 5 hours while stirring. Was done. After completion of the reaction, the micro-autoclave was cooled to room temperature, unreacted gas was purged, and then 2 ml of methanol was added to stop the reaction. After hydrogenating the reaction solution containing the mixed octene to the corresponding octane, gas chromatography (column: Shimadzu Corporation CBP1 capillary 0.25
φ × 50m and 10% SE-30 / Chromosor
b 2m) The product concentration was analyzed by the analytical method. Table of results
Shown in 1.

Example 6 A trans-2-butene dimerization reaction was carried out in the same manner as in Example 1 except that the amount of the phosphine compound used was 0.036 mmol. The results are shown in Table-1.

[0040]

[Table 1]

Example 7 In a 70 ml microautoclave degassed and purged with nitrogen, 11.2 g of trans-2-butene, 0.011 mmol of nickel acetate dissolved in hexane and m-xylene, 0.033 mmol of triphenylphosphine and 0.28 mmol of dichloroethylaluminum was charged. These ratios are: 25: 1 aluminum compound: nickel compound molar ratio, and 0.003: 1.
Corresponds to a nickel (metal): olefin ratio of (g / mol).

Then, hydrogen gas was introduced into the microautoclave until the total pressure reached 3 kg / cm ² · G, and 42
The reaction was carried out at 5 ° C. with stirring for 5 hours. After completion of the reaction, the microautoclave was cooled to room temperature, and after purging unreacted gas, 2 ml of methanol was added to deactivate the catalyst system to stop the reaction. The reaction solution was gas chromatography (column: Shimadzu Corporation CBP1 capillary 0.25 mmφ × 50 m and 10% SE-).
30 / Chromsorb 2m) method was used to analyze the product concentration. The results are shown in Table-2.

Comparative Example 9 In Example 7, 0.011 mmol of bis (triethylphosphine) nickel chloride (Ni (PEt ₃ ) ₂ C was used instead of nickel acetate and triphenylphosphine.
l ₂ ) was used in the same manner except that trans-2-
A butene dimerization reaction was carried out. The results are shown in Table-2.

[0044]

[Table 2] (Note) N is n-octene, M is 3-methylheptene, D
M represents 3,4-dimethylhexene. The octene skeleton distribution is given in wt% analyzed after hydrogenation of mixed octenes to the corresponding octanes.

Example 8 (1) Synthesis of Octenes Trans-fully dehydrated with Molecular Sieve 13X
A n-heptane solution of 1.77 kg of 2-butene and ethylaluminum dichloride (25.45 mmol) was placed in a 5 L internal volume induction induction autoclave made of SUS under a nitrogen atmosphere. Next, in a state where the autoclave was agitated, a xylene solution of nickel acetate (2.05 mmol) and triphenylphosphine (6.15 mmo) which had been charged in a catalyst container previously connected to the autoclave.
The reaction was started by pressurizing the xylene solution of 1) into the autoclave under hydrogen pressure, and the reaction was started at 45 ° C. and the total pressure was 7.5 kg.
/ Cm ² G It was reacted for 3 hours. After the reaction, the catalyst was inactivated by treatment with a 10% sulfuric acid aqueous solution, and then the organic phase was separated. A part of this organic phase was hydrogenated using a 5% Pd / C catalyst, and the skeleton structure of octenes was analyzed by gas chromatography. The results are shown below.

N-Octene 17%, 3-methylheptene 79%, 3,4-dimethylhexene 4% Average degree of branching = 0.87 The selectivity of the mixed octene produced is 87.0% by weight.
Met. The above operation was performed twice.

(2) Collection of octene fraction by distillation The dimerization reaction solution obtained in (1) above was treated with an inner diameter of 30 mm ×
An octene fraction having a column top temperature of up to 127 ° C. was obtained by rectifying at a normal pressure in a five-stage Oldershaw type distillation apparatus and separating a light boiling solvent, a high boiling product and a catalyst component.

(3) Synthesis of INA 600 ml of the octene fraction obtained in the above (2) was placed in a SUS induction stirring autoclave having an internal volume of 1 L under a nitrogen atmosphere.
And Rh (acac) (CO) ₂ (150 mg) and a phosphite compound having the following structure (4.65 g) were added, and H ₂ / CO =
1 with oxo gas at a total pressure of 50 kg / cm ² G
The reaction was carried out at 30 ° C. After 5 hours, the absorption of gas disappeared, so the reactor was cooled to room temperature and, after releasing oxo gas, the whole amount of the reaction liquid was collected. Then pressure 10mmHg
Aldehydes and alcohols were obtained by vacuum single distillation.

[0049]

[Chemical 1] (However, in the formula, + ... tertiary butyl group)

Next, the above-mentioned simple distillation acquisition liquid 600 was placed in a SUS induction type autoclave having an internal volume of 1 L under a nitrogen atmosphere.
ml and 60 g of nickel-chromium supported solid catalyst were charged, the total pressure was maintained at 100 kg / cm ² G with hydrogen gas, and the reaction was carried out at a reaction temperature of 150 ° C. After 4 hours, gas absorption stopped, so the autoclave was cooled, hydrogen gas was released, the whole reaction solution was taken out, and the solid catalyst was removed by filtration, and then with an inner diameter 30 mm × 5 stages Oldershaw type still. Rectified. INA through hydrogenation reaction and rectification
The yield was 95%.

(4) Synthesis and Evaluation of Plasticizer The INA obtained in (3) above and phthalic anhydride were esterified by a conventional method to obtain a plasticizer. Then, a plasticizer / vinyl chloride resin = 67/100 (weight ratio) was mixed to obtain a soft vinyl chloride resin by a conventional method, and various tests were conducted. The results are shown in Table-3.

Example 9 The same as Example 8 except that the same amount of tri-m-tolylphosphine was used as the phosphine compound of the dimerization reaction catalyst instead of triphenylphosphine in the synthesis of the octenes of Example 8. The method was carried out until the synthesis and evaluation of the plasticizer. The results are shown in Table-3.

The results of analyzing the skeleton structure of the octenes obtained by the above dimerization reaction are shown below. n-octene 12.3%, 3-methylheptene 81.4
%, 3,4-dimethylhexene 6.3% Average degree of branching = 0.94 Mixed octene selectivity = 87.5% by weight

Example 10 In the synthesis of octenes of Example 8, o-tolyl diphenylphosphine was used in the same amount instead of triphenylphosphine as the phosphine compound of the dimerization reaction catalyst, and the reaction time was 2 hours. The synthesis and evaluation of the plasticizer were carried out in the same manner as in Example 8. The results are shown in Table-3.

The results of analyzing the skeleton structure of the octenes obtained by the above dimerization reaction are shown below. n-octene 16.0%, 3-methylheptene 79.0
%, 3,4-dimethylhexene 5.0% Average degree of branching = 0.89 Mixed octene selectivity = 89.3% by weight

Example 11 Similar to Example 8, except that n-butyldiphenylphosphine was used in the same amount in place of triphenylphosphine as the phosphine compound of the dimerization reaction catalyst in the synthesis of the octenes of Example 8. The method was carried out until the synthesis and evaluation of the plasticizer. The results are shown in Table-3.

The results of analyzing the skeleton structure of the octenes obtained by the above dimerization reaction are shown below. n-octene 9.4%, 3-methylheptene 80.9
%, 3,4-dimethylhexene 9.7% Average degree of branching = 1.00 Mixed octene selectivity = 83.0% by weight

COMPARATIVE EXAMPLE 10 Synthesis of octenes of Example 8 was carried out except that no phosphine compound was used as a dimerization reaction catalyst and the reaction was carried out at 45 ° C. for 5 hours with a nickel acetate-ethylaluminium dichloride-hydrogen catalyst system. Synthesis and evaluation of the plasticizer were carried out in the same manner as in Example 8. The results are shown in Table-3.

The results of analyzing the skeleton structure of the octenes obtained by the above dimerization reaction are shown below. n-octene 9.0%, 3-methylheptene 60.7
%, 3,4-dimethylhexene 30.2% Average degree of branching = 1.21 Mixed octene selectivity = 96.2% by weight

Comparative Example 11 A plasticizer was prepared in the same manner as in Example 8 except that the same amount of triethylphosphine was used in place of triphenylphosphine as the phosphine compound of the dimerization reaction catalyst in the synthesis of the octenes of Example 8. Was synthesized and evaluated. The results are shown in Table-3.

The results of analyzing the skeleton structure of the octenes obtained by the above dimerization reaction are shown below. n-octene 4.9%, 3-methylheptene 72.1
%, 3,4-dimethylhexene 23.1% Average degree of branching = 1.18 Mixed octene selectivity = 93.4% by weight

Comparative Example 12 Ni / γ-A treated with ethylaluminum dichloride
Using an octene fraction obtained by dimerizing trans-2-butene under a solid catalyst of 1 ₂ O ₃ , synthesis and evaluation of a plasticizer were carried out in the same manner as in Example 8. The results are shown in Table-3. The results of analyzing the skeleton structure of the octenes obtained by the above dimerization reaction are shown below. Normal body 15%, monomethyl body 63%, dimethyl body 2
0%, trimethyl body 2% Average degree of branching = 1.09 Mixed octene selectivity = 83.0% by weight

Example 12 600 ml of the octenes obtained in the above-mentioned Example 8 was placed in a SUS induction-stirring autoclave having an internal volume of 1 L under a nitrogen atmosphere.
And 3.48 g of Co ₂ (CO) ₈ were added, and the total pressure was maintained at 100 kg / cm ² G with an oxo gas having a H ₂ / CO molar ratio of 1, and the reaction was carried out at 130 ° C. After 8 hours, gas absorption ceased, so the reactor was cooled, 3% NaOH aqueous solution was pressure-injected to deactivate the cobalt catalyst, and further cooled, and after oxo gas was released, the reaction liquid was completely taken out and The organic phase was collected after separation. Then, in the same manner as in Example 8,
After collecting aldehyde and alcohol by vacuum distillation,
INA was obtained through hydrogenation reaction and distillation purification. This I
Using NA, it was esterified with phthalic anhydride to synthesize a plasticizer and the performance was evaluated. The results are shown in Table-3.

Comparative Examples 13 and 14 Using the octenes obtained in Comparative Examples 10 and 11,
Synthesis and evaluation of the plasticizer were performed by the method shown in Example 8. The results are shown in Table-3. Comparative Example 15 Using the octenes obtained in Comparative Example 12, synthesis and evaluation of a plasticizer were carried out by the method shown in Example 8. The results are shown in Table-3.

[0065]

[Table 3]

[0066]

[Table 4]

[0067]

EFFECTS OF THE INVENTION According to the method for dimerizing butenes of the present invention, it is possible to economically produce octene-mixed Buddha with a high yield and a low branching degree, and to produce using the octenes. Alcohol shows a comprehensively excellent performance as a plasticizer raw material and has great industrial utility value.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI B01J 31/14 B01J 31/14 X 31/24 31/24 X C07B 61/00 300 C07B 61/00 300 (56) References Kai 58-201730 (JP, A) JP 57-167932 (JP, A) JP 62-158225 (JP, A) JP 64-37 (JP, A) JP 1-160928 ( (58) Fields surveyed (Int.Cl. ⁷ , DB name) C07C 2/36 C07C 11/02 C07C 29/16 C07C 31/125 B01J 31/04 B01J 31/14 B01J 31/24 C07B 61 / 00 300

Claims (2)

(57) [Claims] 1. A method for dimerizing butene containing 2-butene in the presence of a catalyst, wherein (i) a carboxylic acid salt having no nickel-halogen bond and having 1 to 18 carbon atoms.
Organic nickel compounds, (ii) a triarylphosphine and / or monoalkyl-diaryl phosphines, (ii
i) Alkyl aluminum halide compounds and (i
v) A butene dimerization method characterized by using a catalyst system generated in situ from hydrogen. 2. A method for producing an alcohol, which comprises subjecting the octene obtained by the dimerization method according to claim 1 to a hydroformylation reaction and a hydrogenation reaction.