JPH0892134A - Dimerization of olefin - Google Patents

Abstract

PURPOSE: To enable high-selectivity dimerization of an olefin using a specific dimerization catalyst which can proceed the reaction with markedly increased dimerization selectivity and very high reaction activity. CONSTITUTION: When an olefin is dimerized in the presence of a catalyst, a Ni compound such as a nickel carboxylate of 1-8 carbon atoms or nickel bis(acetylacetonate) nickel complex, an organoaluminum compound such as a monoalkylaluminum dihalide, for example, ethylaluminum dichloride and a phosphite of formula I (R<1> , R<2> are each a hydrocarbon; R<3> -R<8> are each an O-free substituent; W is a (substituted) aromatic hydrocarbon; X is 0, 1). The phosphite of formula I is preferably prepared, for example, by reaction of a compound of formula II with phosphorus trichloride in the presence of an amine in a solvent such as toluene, followed by reaction of the resultant intermediate with a phenol or the like.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for dimerizing olefins such as ethylene, propylene, butene, pentene, decene and tetradecene using a specific catalyst.
The olefin dimerization product produced by the dimerization process of the present invention was obtained by hydroformylating this by reacting it with carbon monoxide and hydrogen in the presence of a Group VIII metal-based catalyst such as a Rh catalyst. Further hydrogenation of the aldehyde can give an alcohol. An ester of the alcohol with a carboxylic acid such as phthalic acid is an industrially useful compound because it can be used as a plasticizer for synthetic resins.

[0002]

2. Description of the Related Art A catalyst system for homogeneously dimerizing monoolefins such as ethylene, propylene, butene, pentene, decene and tetradecene has been extensively studied. As a catalyst system, a Ziegler type catalyst having a transition metal as a central catalyst component is usually excellent in terms of dimer selectivity of monoolefin, and among them, a catalyst obtained from a mixture of a nickel compound and an organic aluminum halide is used. In the case of the above, good results were obtained for both dimerization activity and selectivity.

Many studies have also been conducted on a catalyst system in which an organic phosphorus compound is used as a third catalyst component together with the above-mentioned catalyst component, and these catalyst components have an influence on the catalyst activity and product selectivity. It is also known to affect. As a catalyst system using these organic phosphorus compounds in combination,
For example, Japanese Examined Patent Publication (Kokoku) No. 46-34007 discloses a catalyst system comprising a π-allyl type nickel complex, an organic aluminum halide and an organic phosphine. In addition, Japanese Examined Patent Publication No. 48-30241 and Japanese Examined Patent Publication No. 5
No. 0-30041 discloses (R ₄ P) ⁺ (R
₃ PNiX ₃ ) ^- (R is a hydrocarbyl group or hydrogen, X
Represents chlorine, bromine or iodine), NiX ' ₂ (P
R _{'3) 2} (X' is chlorine, bromine or iodine, R 'is
Disclosed is a catalyst system comprising an organic phosphine complex of nickel represented by (indicating an alkyl group). Further, JP-A-5-339174 discloses a catalyst system in which a halogenated phenol, water and sulfonic acids are added as additives to a nickel compound, an alkylaluminum and a trivalent phosphorus compound. The trivalent phosphorus compound in this case is 3 in addition to the organic phosphine as described above.
It discloses the use of valent organic phosphite compounds such as triethyl phosphite, tri-t-butyl phosphite, triphenyl phosphite, tri-p-tolyl phosphite and the like.

[0004]

As described above, various organic phosphorus compounds have been proposed as catalyst components used in the dimerization reaction, but these are not always satisfactory for industrial implementation. The above-mentioned catalyst system has the drawback that it is difficult to handle because it is extremely unstable to air, and that the catalyst synthesis is complicated.
Further, with respect to the above catalyst system, it is necessary to separately synthesize a complicated nickel complex, so that industrial implementation is difficult. Furthermore, in the above catalyst system, the dimerization reaction proceeds with high activity for lower α-olefins such as ethylene and propylene, but the dimerization activity for internal olefins, for example, reaction substrates such as 2-butene. Is not sufficient and is not satisfactory in terms of catalytic efficiency for a raw material substrate containing an internal olefin.

As described above, catalyst systems using various organic phosphorus compounds as co-catalysts have been proposed as olefin dimerization reaction catalysts. However, the stability of the catalyst, the synthesis method, the catalyst efficiency,
Furthermore, in terms of product selectivity, it is not always satisfactory for industrial practice, and there are still problems. Therefore, it is a problem to be solved by the present invention to develop a dimerization reaction catalyst system excellent in catalyst efficiency and target product selectivity.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems in the olefin dimerization method, the present inventors have found that a specific dimerization catalyst enhances the dimerization product selectivity. The present invention has been completed by finding that the reaction can proceed with extremely high activity. That is, the present invention, when dimerizing an olefin in the presence of a catalyst, as a catalyst,
Nickel compounds, organoaluminum compounds and general formula (I):

[0007]

[Chemical 2]

(In the formula, R ¹ and R ² represent a hydrocarbon group and may be different from each other, and R ^{3 to} R ⁸ represent a substituent containing no oxygen atom or a hydrogen atom and may be different from each other; W is a substituted or unsubstituted aromatic hydrocarbon group, and x is 0 or 1). A olefin dimerization method characterized by using a phosphite compound .

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. Examples of the olefin used in the dimerization method of the present invention include ethylene, propylene, butenes, pentenes, hexenes, decenes, tetradecenes, and the like, or a mixture thereof. As mentioned above, the resulting olefin obtained by the dimerization method of the present invention can be converted into an alcohol by hydroformylation and hydrogenation, and this alcohol can be further esterified and used as a plasticizer. In consideration of application to alcohol for plasticizer, as the olefin as a raw material, propylene, butenes, single olefins such as lower olefins such as pentene and a mixture thereof are preferable,
Butenes are particularly preferable.

The butenes include butene fraction having a high n-butene content after separating butadiene and isobutylene from C ₄ fraction (BB fraction) obtained by thermal decomposition of hydrocarbon oil such as naphtha. It can be used suitably. 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.
-A butene fraction having a high butene content can also be preferably used. The above-mentioned butenes usually contain a large amount of 2-butene which is an internal olefin in addition to 1-butene, but the dimerization method of the present invention has a sufficiently high activity for an internal olefin substrate such as 2-butene. Express.

The dimerization reaction catalyst used in the present invention is
(I) nickel compound, (ii) organoaluminum compound, and (iii) general formula (I):

[0012]

[Chemical 3]

(In the formula, R ¹ and R ² represent a hydrocarbon group and may be different from each other, and R ^{3 to} R ⁸ represent a substituent containing no oxygen atom or a hydrogen atom and may be different from each other; W represents a substituted or unsubstituted aromatic hydrocarbon group, and x is 0 or 1) and is a catalyst system containing a phosphite compound.

The nickel compound used in the present catalyst system is not particularly limited. For example, nickel carboxylates such as nickel formate, nickel acetate, nickel octoate, nickel dodecanoate, nickel naphthenate, nickel oleate and nickel benzoate, bis (acetylacetonato) nickel, bis (cyclooctadiene) nickel. Nickel complex compounds such as nickel, inorganic nickel salts such as nickel chloride, nickel bromide, nickel iodide, nickel nitrate, nickel sulfate, etc. are easily available nickel compounds. A nickel carboxylate salt of 1 to 18 and a bis (acetylacetonato) nickel complex compound are preferably used.

The organoaluminum compound is also not particularly limited. For example, a trialkylaluminum compound represented by the general formula AlR ₃ (wherein R represents an alkyl group having 1 to 5 carbon atoms), specifically, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri- n-butylaluminum, triisopropylaluminum, triisobutylaluminum, tri-t-butylaluminum, or the like, or the general formula AlR ₂ X, AlRX ₂ , Al ₂ R ₃ X ₃ (where R is an alkyl having 1 to 5 carbon atoms). Represents a group and X represents a halogen atom), and a monohalogeno-dialkylaluminum, dihalogeno-monoalkylaluminum or sesquihalogeno-alkylaluminum compound, specifically diethylaluminum monochloride, ethylaluminum dichloride, ethyl Rumi um sesquichloride, propyl aluminum dichloride, isobutyl aluminum dichloride and the like, more trialkylaluminum or halogeno-alkyl aluminum with the can be mentioned partially hydrolyzed organic aluminoxane compounds. Among these organic aluminum compounds, halogenated alkyl aluminum compounds are preferable,
Among them, dihalogeno such as ethyl aluminum dichloride
Monoalkylaluminum compounds are more preferred.

In the method of the present invention, the basic catalyst system composed of a nickel compound and an organoaluminum compound is allowed to coexist with the specific phosphite compound represented by the above-mentioned general formula (I), so that the catalyst system is higher than the conventional catalyst system. An active and highly selective mixture of dimerized olefins can be obtained. When the catalyst component does not include the phosphite compound, or other phosphite compounds such as triphenyl phosphite and triethyl phosphite are represented by the general formula (I) of the method of the present invention in the phosphite structure. When a phosphite compound that does not have such a cyclic structure and does not have a sterically hindering substituent near the oxygen atom of the P—O bond is used, the dimerization activity is low and the catalytic performance is Not necessarily satisfactory.

The phosphite compound used in the present invention is represented by the above general formula (I). In the above formula, R ^{3 to} R ⁸
The group represented by may be a group containing no oxygen atom or a hydrogen atom, and examples of the group containing no oxygen atom include an alkyl group, an aryl group, a cycloalkyl group, and a halogen atom. Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a nonyl group,
An alkyl group having 1 to 20 carbon atoms such as octadecyl group, an aryl group having 6 to 12 carbon atoms such as phenyl group and naphthyl group,
Examples thereof include a cycloalkyl group having 4 to 12 carbon atoms such as a cyclohexyl group and a halogen atom such as a chlorine atom and a bromine atom. Among these, an alkyl group, particularly an alkyl group having 1 to 20 carbon atoms is preferable. The groups represented by R ^{3 to} R ⁸ may be the same or different. Considering the ease of synthesizing the phosphite compound, R ³ , R ⁵ , R ⁶ ,
R ⁸ is a hydrogen atom, and R ⁴ and R ⁷ have 1 to 2 carbon atoms.
Especially preferred is the combination of 0 alkyl groups.

In the phosphite compound used in the present invention, having a hydrocarbon group represented by R ¹ and R ² in the above-mentioned general formula (I) is effective for enhancing the dimerization reaction activity. Is extremely important. Examples of the hydrocarbon group of R ¹ and R ² include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, a cycloalkyl group having 4 to 12 carbon atoms, and the like. Depending on the steric hindrance of the group represented by W in the general formula (I)
The bulky R ¹ and R ² substituents are preferred.
Therefore, a branched alkyl group, preferably a branched alkyl group having 3 to 10 carbon atoms, is used as the hydrocarbon group for R ¹ and R ² , specifically, i-propyl group, s-butyl group, t- Butyl group, s-amyl group, t-amyl group, t-
Hexyl group, cyclohexyl group, 1-methylcyclohexyl group and the like are used. Further, R ¹ and R ² may be the same or different groups.

In the above general formula (I), W represents an aromatic hydrocarbon group, and the aromatic hydrocarbon group is
Examples thereof include a phenyl group, a 2-naphthyl group, an anthryl group and the like. This aromatic hydrocarbon group may have no substituent, but it is preferably one having a substituent, and among them, a phenyl group having a substituent is preferable.

Examples of the substituent in the aromatic hydrocarbon group include an alkyl group, an aryl group, a cycloalkyl group, a halogen atom and the like. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, 1 to 2 carbon atoms such as hexyl group, octyl group, nonyl group and octadecyl group
0 carbon number such as alkyl group, phenyl group, naphthyl group, etc.
~ 12 carbon atoms such as aryl group and cyclohexyl group ~
12 cycloalkyl groups, halogen atoms such as chlorine atom and bromine atom, and the like. Among these, an alkyl group, particularly an alkyl group having 1 to 20 carbon atoms is preferable.

In particular, in the above-mentioned aromatic hydrocarbon group represented by W, the carbon atom adjacent to the carbon atom bonded to the oxygen atom constituting the P—O bond (for example, ortho position in phenyl group: hereinafter, other than phenyl group) Including the case, it is preferable to have a substituent at the ortho position). Examples of the substituent include a methyl group, ethyl group, i-propyl group, s-butyl group, t-butyl group, s-amyl group, t
Examples of the substituent include an amyl group, a t-hexyl group, a cyclohexyl group, and a phenyl group.
A substituent having 10 substituents (for example, a hydrocarbon group having 3 to 10 carbon atoms) is preferable for enhancing the dimerization reaction activity.

When R ¹ and R ² are bulky substituents and the substituent at the ortho position of W is a methyl group, an ethyl group, an i-propyl group or a s-butyl group, for example, butenes When the dimerization reaction is performed, the content of dimethylhexene in the produced octenes is reduced, and the average branching degree is reduced. Therefore, the produced olefin is hydroformylated, further hydrogenated to induce an alcohol, and the alcohol is reacted with a carboxylic acid such as phthalic acid to be esterified to obtain excellent performance when used as a plasticizer for a synthetic resin. Indicates.

In the general formula (I),

[0024]

[Chemical 4]

The value of x in the cross-linking group represented by is 0 or 1, and in both cases the activity and selectivity are excellent, but among them, the distribution and selectivity of the dimerization product produced depending on the value of x are large. Change. For example, when the dimerization reaction of butenes is carried out with the catalyst system used in the present invention, x =
When 0, that is, when the bridging group is a single bond, octenes having relatively few branches are formed with high activity and high selectivity, whereas x
= 1, that is, when the bridging group is a methylene group, the degree of branching of the produced octenes is slightly high, but the selectivity of the dimerization product is further improved, and the selectivity is extremely high even under the conditions of high conversion rate. . This has great industrial utility value in that the target product can be produced economically.

The details of how the phosphite compound represented by the general formula (I) acts on the structure or reactivity of the dimerization catalyst are unknown, but in the general formula (I) In each of the two bridged substituted phenylene groups and the aromatic hydrocarbon group represented by W, having a substituent at the ortho position suppresses an undesired reaction with the organoaluminum compound as a Lewis acid. As a result, it is considered that the stable and active catalyst structure is retained.

The method for preparing the phosphite compound represented by the general formula (I) is not particularly limited,
For example, the general formula (II):

[0028]

[Chemical 5]

(Wherein R ^{1 to} R ⁸ and x have the same meaning as in formula (I)) and phosphorus trichloride are reacted in the presence of an amine compound in a solvent such as toluene to give an intermediate compound. Body (III):

[0030]

[Chemical 6]

(Wherein R ^{1 to} R ⁸ and x have the same meanings as in the general formula (I)), the intermediate (III) is converted to the general formula (IV):

[0032]

Embedded image W-OH (IV)

It can be easily produced by reacting with a compound represented by the formula (wherein W has the same meaning as in formula (I)) to give a corresponding phosphite compound.

Examples of the compound represented by the above general formula (IV) include phenol, 2-methylphenol, 2,4-dimethylphenol, 2,4,6-trimethylphenol, 2-t-butylphenol, 2, 4-
Di-t-butylphenol, 2-s-butylphenol, 2,4-di-s-butylphenol, 2-isopropylphenol, 2-t-amylphenol, 2-s-
Amylphenol, 2-t-hexylphenol, 2,
4-di-t-amylphenol, 6-t-butyl-2,
4-xylenol, 2,4-dichlorophenol, 2,
4,6-Trichlorophenol, 3-t-butyl-4-
Hydroxybiphenyl, 2-t-butyl-p-cresol, 2-hydroxybiphenyl, 2-cyclohexylphenol, 2-naphthol, 3-isopropyl-2-naphthol, 3,6-diisopropyl-2-naphthol,
3-t-butyl-2-naphthol, 3,6-di-t-butyl-2-naphthol, 3,6-di-s-butyl-2-
Naphthol, 3-t-amyl-2-naphthol, 3,6
-Di-t-amyl-2-naphthol, 3-t-hexyl-2-naphthol, 3-phenyl-2-naphthol,
3,6-diphenyl-2-naphthol, 3-cyclohexyl-2-naphthol and the like can be mentioned.

Examples of the compound represented by the above general formula (II) include 3,3 ', 5,5'-tetramethyl-2,2'-biphenyldiol and 5,5'-dimethyl-3. , 3'-Diethyl-2,2'-biphenyldiol, 5,5'-dimethyl-3,3'-di-t-butyl-2,2'-biphenyldiol, 5,5'-diethyl-3,3 '-Di-t-butyl-2,2'-biphenyldiol, 5,5'-dichloro-3,3'-di-t-butyl-2,2'-biphenyldiol, 3,3', 5
5'-tetra-t-butyl-2,2'-biphenyldiol, 5,5'-di-t-butyl-3,3'-diphenyl-2,2'-biphenyldiol, 5,5'-di- t
-Butyl-3,3'-diisopropyl-2,2'-biphenyldiol, 5,5'-dimethyl-3,3'-di-
t-amyl-2,2'-biphenyldiol, 5,5 '
-Di-t-hexyl-3,3'-di-t-butyl-2,
2'-biphenyldiol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2 '
-Methylenebis (4-ethyl-6-t-butylphenol, 2,2'-methylenebis (4,6-diisopropylphenol), 2,2'-methylenebis (4,6-di-
t-butylphenol), 2,2'-methylenebis (4
-Chloro-6-t-butylphenol) and the like.

Typical examples of the phosphite compound represented by the general formula (I) used in the present invention are shown below.

[0037]

Embedded image

[0038]

[Chemical 9]

[0039]

[Chemical 10]

[0040]

[Chemical 11]

[0041]

[Chemical 12]

[0042]

[Chemical 13]

[0043]

Embedded image

[0044]

[Chemical 15]

[0045]

[Chemical 16]

[0046]

[Chemical 17]

[0047]

[Chemical 18]

Here, the symbols representing the substituents in the above structural formulas are, respectively,

[0049]

[Chemical 19]

Represents In the method of the present invention, the olefin dimerization reaction is carried out in the presence of a catalyst system containing the nickel compound, the organoaluminum compound and the phosphite compound represented by the general formula (I). At this time, the coexistence of hydrogen in the reaction system can further improve the catalytic activity. Although the mechanism is not clear, various assumptions such as removal of impurities in the reaction system (for example, reaction-inhibiting substances such as conjugated dienes), promotion of generation of catalytically active species, contribution of catalyst stability, etc. are considered. The coexistence clearly increases the dimerization reaction activity. The amount used is not particularly limited and may be an amount that produces a preferable result on the catalytic activity, but usually, the hydrogen partial pressure is 0.01 to 30 kg / cm ² , preferably 0.1 to 20.
It is kg / cm ² .

In the olefin dimerization reaction carried out in the present invention, the nickel compound, the organoaluminum compound and the catalyst components of the phosphite compound represented by the general formula (I) may be mixed in any order. However, it is preferable to use a nickel compound and a phosphite compound represented by the general formula (I) by mixing them in advance, or to use them as a complex thereof, and to use these Ni-P compound and the organoaluminum compound as an olefin, For example, simultaneous contact in the presence of butenes is preferred in order to obtain a highly active dimerization product such as octenes. this is,
It is considered that the organoaluminum compound generally works as a strong reducing agent, and thus the nickel compound is reduced and the activity is reduced when an electron-donating ligand such as an olefin is not present.

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, 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 phosphite compound represented by the general formula (I) to the nickel compound is usually 0.1-20, preferably 1-5.

If the molar ratio of the organoaluminum compound to the nickel compound in the catalyst is too low, it reacts with a small amount of oxygen, water, etc. present in the dimerization reaction system, and the catalytic activity sharply decreases. Further, even if the above molar ratio is higher than necessary, the dimerization activity is not significantly improved, and it is not economically advantageous. If the molar ratio of the phosphite compound to the nickel compound is too low, the dimerization activity is lowered and the degree of branching of the produced olefin is increased. On the other hand, if it is too high, the dimerization activity is lowered, depending on the amount of the organic aluminum compound present, and it is not economically advantageous.

As the reaction conditions for the dimerization carried out in the present invention, the reaction temperature is usually -10 to 100 ° C, preferably 0.
The temperature is -80 ° C, and more preferably 10-80 ° C, which is appropriately set depending on the productivity of the process and the stability of the nickel compound and the organoaluminum compound used. It is effective that the reaction pressure is such that the catalyst component is sufficiently present in the liquid phase of the olefin such as butenes.
It is preferably about 50 kg / cm ² . Further, in the dimerization method of the present invention, methane, ethane, propane,
It can be carried out even if it contains a paraffinic hydrocarbon such as butane or an inert gas such as nitrogen, argon or carbon dioxide. The dimerization reaction system may be a continuous system or a batch system.

After the completion of the reaction, the catalyst is inactivated by a known method, for example, ammonia water, an aqueous solution of sodium hydroxide or an aqueous solution of sulfuric acid, and then the catalyst is removed, and then an unconverted olefin and a reaction solvent are formed by a distillation operation. It is possible to separate and acquire things. As mentioned above, the dimerization product of the olefin produced by the dimerization method of the present invention is obtained by reacting it with carbon monoxide and hydrogen in the presence of a Group VIII metal-based catalyst such as Rh catalyst. The resulting aldehyde can be converted to an alcohol by further hydrogenation.

The above hydroformylation reaction is carried out according to a conventional method. The hydroformylation reaction conditions are also not particularly critical, and any conventionally known rhodium method or cobalt method can be used. In the case of the rhodium method, the rhodium source may be an organic salt such as Rh (OAc) ₃ or Rh (N
Inorganic salts such as O ₃ ) ₃ and RhCl ₃ or Rh (ac
ac) (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 (COD)] ₂ (where Ac is an acetyl group,
acac represents an acetylacetonate group, and COD represents cyclooctadiene. ) And other complexes can be used.

As the cobalt source in the case of the cobalt method,
Organic acid salts such as cobalt laurate, Co (NO₃)₂
In addition to inorganic acid salts such as Co₂(CO)₈, CoH (C
O) _FourA complex such as can be used. The reaction pressure is
Normal pressure-300 kg / cm²G, the reaction temperature is
Usually 50 ℃ ~ 150 ℃, H₂The molar ratio of CO / CO
Usually 1 to 10, the catalyst concentration is usually 0.1 to 1000 p
The condition of pm (metal atom conversion) is adopted. As a ligand
Triphenylphosphine, triphenylphosphine
Organophosphorus compounds and their oxides such as
The molar ratio is usually 1 to 1000
It

A reaction solvent may not be used, but if necessary, a solvent inert to the reaction, such as benzene, 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.

Next, an alcohol is produced by a hydrogenation reaction of the obtained aldehyde, which can be carried out by a usual method. That is, a normal hydrogenation catalyst such as Ni, Cr, Cu is used, and the reaction pressure is usually from atmospheric pressure to 150 kg.
/ Cm ² G, and the reaction temperature is usually 40 ° C to 300 ° C. The alcohol can then be obtained by conventional distillation purification.

The alcohol obtained as described above, particularly the alcohol having 9 carbon atoms (so-called isononyl alcohol; INA) produced from butenes as a raw material is treated with an acid such as phthalic anhydride or adipic acid by a conventional method. A plasticizer (for example, a phthalate plasticizer) can be obtained by performing an esterification reaction with and then purifying, and the obtained plasticizer has excellent performance.

[0061]

EXAMPLES Next, specific embodiments of the present invention will be described in more detail with reference to Examples. However, the present invention does not exceed the gist of the invention.
The present invention is not limited to the examples below. Example 1 8.28 mg of nickel octanoate was placed in a stainless steel microautoclave having an internal volume of 70 ml which was degassed and then replaced with nitrogen.
And an m-xylene solution containing 3 moles (P / Ni = 3) of the phosphite compound (10) per mole of nickel atom, and 38.1 mg of dichloroethylaluminum (A).
and a pentane solution containing 1 / Ni = 12.5) were charged under a nitrogen atmosphere. Next, 20 ml of trans-2-butene was charged, the microautoclave was sealed, and the reaction was carried out by stirring at 40 ° C. for 5 hours. After completion of the reaction, the micro-autoclave was cooled to room temperature, and after purging unreacted gas, 2 ml of methanol was added to stop the reaction.

Gas chromatography (column; CBP1 capillary 0.2 manufactured by Shimadzu Corporation) for the reaction liquid
5φ x 50m and 10% SE-30 / Chromos
orb 2m) was analyzed for product concentration. The results are shown in Table 1.

Comparative Example 1 A trans-2-butene dimerization reaction was carried out in the same manner as in Example 1 except that the phosphite compound was not added. The reaction results are shown in Table 1.

Comparative Examples 2 and 3 In Example 1, triphenyl phosphite and triethyl phosphite were used instead of the phosphite compound (10) in an amount of 3 mol (P / Ni) per mol of nickel atom.
= 2), the dimerization reaction of trans-2-butene was carried out in the same manner as above. The reaction results are shown in Table 1.

Examples 2 to 10 Various phosphite compounds shown in Table 1 were used in place of the phosphite compound (10) in Example 1 at a ratio of 3 mol phosphorus atom (P / Ni = 3) per 1 mol nickel atom. The dimerization reaction of trans-2-butene was carried out in the same manner except that it was used. The reaction results are shown in Table 1.

Comparative Example 4 Except that the phosphite compound shown in Table 1 was used in place of the phosphite compound (9) in Example 7 in a ratio of 3 mol (P / Ni = 3) per mol of nickel atom. The dimerization reaction of trans-2-butene was carried out in the same manner. The reaction results are shown in Table 1.

Examples 11 to 16 In place of the phosphite compound (10) in Example 1, various phosphite compounds shown in Table 1 were used at a ratio of 1 mol of phosphorus atom (P / Ni = 1) per 1 mol of nickel atom. A trans-2-butene dimerization reaction was carried out in the same manner as above except that the dimerization reaction was carried out at 60 ° C. for 3 hours. The reaction results are shown in Table 1.

Example 17 In Example 12, ethyl aluminum sesquichloride was used instead of dichloroethylaluminum in an amount of 25 mol of aluminum atom per 1 mol of nickel atom (Al / Ni = 25).
In the same manner except that it was used in the ratio of
A butene dimerization reaction was carried out. The reaction results are shown in Table 1.

Example 18 Trans-2-butene was prepared in the same manner as in Example 1 except that trans-2-butene was charged and then hydrogen gas was injected until the total pressure became 5 kg / cm ² G. The dimerization reaction was carried out. The reaction results are shown in Table 1.

Comparative Example 5 A trans-2-butene dimerization reaction was carried out in the same manner as in Example 18 except that the phosphite compound was not added. The reaction results are shown in Table 1.

Comparative Examples 6 and 7 Instead of the phosphite compound (10) in Example 18, triphenyl phosphite and triethyl phosphite were used in an amount of 3 mol per mol of nickel atom (P / Ni =
A dimerization reaction of trans-2-butene was carried out in the same manner except that it was used in the ratio of 3). Table of reaction results
It is shown in FIG.

Examples 19 to 21 Instead of the phosphite compound (10) in Example 18, various phosphite compounds shown in Table 1 were used in a ratio of 3 mol (P / Ni = 3) per mol of nickel atom. A dimerization reaction of trans-2-butene was carried out in the same manner except that the above was performed. The reaction results are shown in Table 1.

Example 22 After degassing, 3.76 ml of a heptane solution of dichloroethylaluminum having a concentration of 0.2 mol / L was charged in a 300 ml stainless steel autoclave whose internal volume was replaced with nitrogen under a nitrogen atmosphere, and then trans-2. -Butene 29.
2 g (520 mmol) was injected under pressure, and the temperature of the autoclave was raised to 60 ° C with stirring. After reaching 60 ° C., 20.7 mg of nickel octoate and the phosphite compound (19) were added in an amount of 1 mol (P / N) per 1 mol of nickel atom.
A heptane solution containing i = 1) was injected under pressure with purified hydrogen to start the reaction, and the reaction was performed for 1 hour. The reaction results are shown in Table 1.

Example 23 After degassing, 25.6 m of a heptane solution of dichloroethylaluminum having a concentration of 0.1 mol / L was placed in a stainless steel induction stirring autoclave having an internal volume of 5 liters, which was purged with nitrogen.
1 and cyclohexane (100 ml) were charged under a dry nitrogen atmosphere, and then 1.78 kg (31.72 mol) of 1-butene dehydrated by molecular sieves was injected under pressure.

With stirring at room temperature, 20.5 ml of a solution of nickel octenate in heptane having a concentration of 0.1 mol / L and the above-mentioned phosphite compound (19) in an amount of 1 mol per mol of nickel atom (P / Ni = 1) are contained in heptane. The solution was pressed into the autoclave with dry nitrogen to initiate the reaction.
Although an increase in temperature and pressure in the autoclave was immediately observed, the temperature was kept at 60 ° C. by appropriately using an external cooler and an external heater, and the reaction was carried out for 3 hours. After 3 hours,
50 ml of methanol was pressed into the autoclave to stop the reaction, and after cooling to room temperature, unreacted gas was purged and the product concentration of the internal solution was analyzed by gas chromatography. Table 2 shows the results.

Example 24 In the same manner as in Example 23 except that the catalyst components of dichloroethylaluminum, nickel octanoate and the phosphite compound were premixed and 1-butene was introduced under pressure to start the reaction. A butene dimerization reaction was carried out. Table 2 shows the results. As can be seen from Table-2, the effect of higher activity and higher selectivity than that of the prior art can be obtained regardless of the order of contact of the catalyst, but the more excellent effect can be obtained by contacting the catalyst in the presence of olefin. can get.

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

[Table 3]

[0080]

[Table 4]

[0081]

[Table 5]

[0082]

[Table 6]

[0083]

[Table 7]

[0084]

[Table 8]

[0085]

INDUSTRIAL APPLICABILITY According to the present invention, an olefin can be dimerized with high activity to obtain a dimerized product with high selectivity.

Claims (1)

[Claims] 1. When dimerizing an olefin in the presence of a catalyst, a nickel compound, an organoaluminum compound and a compound represented by the general formula (I): (In the formula, R ¹ and R ² represent a hydrocarbon group and may be different from each other, and R ^{3 to} R ⁸ represent a substituent containing no oxygen atom or a hydrogen atom and may be different from each other;
Represents a substituted or unsubstituted aromatic hydrocarbon group, and x is 0
Or 1) is used, the dimerization method of the olefin characterized by using the phosphite compound.