JPS62158225A - Method for dimerizing lower alpha-olefin - Google Patents

Abstract

PURPOSE:To dimerize a lower alpha-olefin industrially advantageously, by using a catalyst consisting of an organic salt or complex compound of nickel, a trialkylaluminum, a specific trivalent phosphorus compound and a fluorinated isopropanol. CONSTITUTION:In dimerizing a lower alpha-olefin, a catalyst consisting of (A) an organic salt or complex compound of nickel, (B) a trialkylaluminum, (C) one or more compounds shown by formula PR<1>R<2>R<3>, P(NR2<1>)3 or P(OR<1>)3 (R<1>-R<3> are alkyl, cycloalkyl or phenyl) and (D) a compound shown by formula I (m and n are integers to show 4<=m+n<=6) is used and, if necessary, (E) 0- <equimolar amount based on the component B of one or more compounds shown by formula II or R<4>R<5>R<6>CX (X is halogen; R<4>-R<6> are lower alkyl; n is 1-3 numerical value) is further utilized as a catalytic activity auxiliary so that corrosive properties of device and heterogeneity of catalyst in the reaction system are improved and improvement in catalytic efficiency and selectivity is contrived.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for dimerizing lower α-olefins. Specifically, the present invention relates to a method for dimerizing lower α-olefins, which is characterized by using a new nickel-containing Ziegler type catalyst.

<Prior Art> Dimers of lower α-olefins, such as ethylene, propylene, and butene dimers, are used as basic raw materials for agricultural chemicals, fragrances, chemical products, etc., and as raw materials for biomolecular compounds. As a manufacturing method thereof, for example, the following dimerization method using a nickel-containing Ziegler type catalyst is known.

B. Catalyst consisting of π-allyl nickel complex/organoaluminium halide/organophosphine (Japanese Patent Publication No. 46-8
Publication No. 4007).

B. Catalyst consisting of nickel salt/organoaluminum halide/organophosphine (Japanese Patent Publication No. 47-22807); C. Catalyst consisting of nickel salt/trialkyl aluminum/organophosphine/halogenated phenol/water (Japanese Patent Application Laid-open No. Sho 57) (Publication No. 167982), <Problems to be solved by the invention> However, since the above method (a) uses a π-allylic nickel complex, which is unstable in air, as the nickel component, its handling is difficult. Not only is this extremely inconvenient, but it also has the disadvantage that such a complex must be synthesized separately using complicated means.

In addition, since both methods use organoaluminium halides as the aluminum component, halogen atoms bonded to aluminum atoms are likely to be desorbed as HC/ etc. due to the influence of moisture in the system, leading to corrosion of the equipment. Another problem is that when propylene, for example, is used as the lower olefin, the fraction of 2°8-dimethylbutenes (hereinafter abbreviated as DMBS fraction) in the dimer produced does not show a sufficient value. There was a spot between them.

On the other hand, the blind method solves the above problem,
Although this was proposed by the present inventors, a phenomenon has occurred in which the heat removal ability of the cooling heat exchanger gradually decreases due to long-term operation. When we analyzed this phenomenon, we found that
It was found that the minute amount of precipitate on the surface of the heat exchanger was derived from the catalyst, and it was found that the method (c) was not necessarily fully satisfactory in terms of the uniformity of the catalyst in the reaction system.

The known methods have various problems as mentioned above, and are not satisfactory as an industrial method for dimurizing α-olefins.

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have repeatedly investigated the catalyst system, and as a result, we have developed a method for solving the problems described above. The inventors have discovered that by using a specific fluorinated isopropanol, the problems of known methods can be improved, such as improving the homogeneity of the reaction system, and the catalyst efficiency and selectivity can also be improved. completed.

That is, the present invention uses a Nishi nickel organic salt or complex compound, trialkylaluminum, (C) -e formula (1) i (n) or (III) as a catalyst when nylating a lower α-olefin.
P R' R2R3 (1) P (OR' )3 (Ill) (wherein, R
, R and R each independently represent an alkyl, cycloalkyl or phenyl group) At least one octavalent phosphorus compound represented by the general formula (IV) CFmHa -m -CH-CFn Ha -n
(IV) ♂H (where nl and n represent integers satisfying 4≦m+n≦6) Using a catalyst consisting of four components of fluorinated isopropanol, 01! General formula ν) or (Vl) as Il medium active auxiliary agent
σCHa-n
An industrially excellent method for duplexing lower α-olefins, characterized in that at least one halogen compound represented by (n represents a numerical value of 1 to 8) is used in an amount of 0 to less than the equimolar amount based on the trialkylaluminium. It provides:

Examples of organic acid salts of nickel in the catalyst component used in the present invention include nickel carboxylates such as nickel naphthenate, nickel octylate, nickel stearate, nickel formate, nickel acetate, nickel benzoate, and nickel oxalate. Acid salts are listed. Examples of complex compounds of nickel include bis-acetylacetonate nickel and bis-dimethylglyoximate nickel, which are easy to prepare and stable. In addition, nickel compounds that have previously formed complex compounds with organic phosphines as O components can also be used, such as Evahis tricyclohexylphosphine nickel chloride, bis triisopropylphosphine nickel chloride, bis triphenylphosphine nickel. Chloride, bis-tris-dimethylaminophosphine-nickel chloride, bis-tris-dimethylaminophosphine-nickel chloride, and compounds in which the chloride in these is converted to bromide can also be used.

In addition, catalyst components (such as trimethylaluminum, triethylaluminum, triethylaluminum,
Examples include tri-n-propylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-n-butylaluminum, tri-n-pentylaluminium, )-IJ-n-hexylaluminum, tricyclohexylaluminum, and the like.

Of the trivalent phosphorus compounds with catalyst component 0, general formula (1) P
The organic phosphine compounds represented by RI R2R" include trimethylphosphine, l-ethylphosphine,
Tri-n-propylphosphine, trimy propylphosphine, tri-n-butylphosphine, trimy-butylphosphine, tri-t-butylphosphine, tri-5eC-butylphosphine, tricyclopropylphosphine, tricyclohexylphosphine, triphenylphosphine, tri-p- Tolylphosphine, Tri-p-methoxyphenylphosphine, Tri-2.4.6-t-limethylphenylphosphine, Phenyl-di-mi-propylphosphine, Ethyl-di-mi-propylphosphine,
Examples include ethyl-di-t-butylphosphine, ethyl-dicyclohexylphosphine, methylpropylphenylphosphine, methylphenylbenzylphosphine, and the like.

The aminophosphine compounds represented by the general formula (n)P(NR'□)3 include tris-dimethylaminophosphine, tris-diethylaminophosphine, tris-di-
n-propylaminophosphine, tris-dimeypropylaminophosphine, tris-di-n-butylaminophosphine, tris-dimeybutylaminophosphine, tris-di-t-butylaminophosphine, tris.
Examples include di-cyclohexylaminophosphine.

Examples of the phosphite compound represented by the general formula ((2)P(ORI)3) include trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, tri-n-propyl phosphite, tri-n-butyl phosphite, and tri-n-butyl phosphite. Mebutyl phosphite, Tory-t-
Examples include butyl phosphite, tricyclohexyl phosphite, triphenyl phosphite, tri-T)-)lylphosphite, tri-p-methoxyphenyl phosphite, etc.

These octavalent phosphorus compounds have the greatest effect on the isomer distribution of the α-olefin dipole.

For example, when it is desired to obtain a high fraction of 2,8-dimethylbutenes by duplication of propylene, it is preferable to use organic phosphines such as streamy propylphosphine, tricyclohexylphosphine, and tri-5eC-butylphosphine.

In addition, the fluorinated isopropanol represented by the general formula (3) with catalyst component 0 includes 1,1,8.8-tetrafluoroisopropanol, 1,1,1.8-tetrafluoroisopropanol, 1,1,1゜3 .3-pentafluoroisopropanol, 1.1,1,8,8.8-hexafluoroisopropanol, etc. are used. Among these, 1,1,1,8,3,8-hexafluoroisopropanol is particularly preferred.

Such a fluorinated alcohol is an essential component for the present catalyst system to exhibit duplexing viscosity, and without this alcohol, it does not substantially exhibit α-olefin duplexing activity. Furthermore, by changing the amount of alcohol added, it is possible to control the distribution of double bond isomers in the produced olefin cylinder. For example, by doubling propylene, 2.3-
When selectively obtaining dimethylbutenes, if the amount of fluorinated alcohol added is small, 2,8-dimethylbutene-1 will be obtained, but if the amount added is increased, 2,3-dimethylbutene-1 will be obtained.
2 is obtained.

Next, in the present invention, compounds represented by the general formula (V) that can be added as active aids include pensitrichloride, benzalchloride, benzylchloride, benzotribromide, benzalbromide, and benzyl bromide. etc. will be listed. Examples of the compound represented by the general formula (b) include tert-butyl chloride, tert-butyl chloride,
Examples include t-amyl chloride, tert-hebutyl chloride, tert-butyl bromide, tert-amyl bromide, tert-heptyl bromide, and the like. Although the catalyst system of the present invention has sufficient duplexing activity even without these active aids, such active aids may be effective in some cases. however.

The active aid is used in an amount less than the same mole as the trialkylaluminum as component (B), preferably 0.5 mole or less. If the activation aid is used in an amount equal to or more than the mole of trialkylaluminium, the selectivity of DMBS in the di-component will decrease, for example in the case of synthesis of 2,3-dimethylbutenes by diconversion of propylene. , one of the features of the invention is lost.

The catalyst system used in the present invention can be used stably if a lower α-olefin, which is a reaction raw material, is present during catalyst preparation, but it is preferable to prepare it in the presence of a chain conjugated diolefin.

Such catalyst stabilizing aids include butadiene, isoprene,
(2) Military diolefins such as 8-pentadiene are mentioned, and the amount added is 200 times or less by mole of the nickel compound as the western component.

Even if more than this amount is added, there is no substantial change in the stabilizing effect.

There is no particular restriction on the mixing order of catalyst components in the present invention.
They may be mixed in any order. To give a preferred example, a tetranickel compound, (C) an octavalent phosphorus compound, (B) a trialkylaluminium, and (D
) Adding and mixing fluorinated isopropanol in this order, or (A), (C), (D), and (B) in this order, or (C), (A),
(B) and (D), etc. The general formula of the active auxiliary agent (
When adding the components shown in v) and (VI), there are no special restrictions on the mixing order.

The molar ratios of the catalyst components are typically selected from the following ranges: (B
)/(A) = 2-5001 preferably 5-100 molar ratio, (C)/(A) = o, 1-50·, preferably 0.5-20 molar ratio, (L)/(B) = 0.2
-10, preferably 0.5-5 molar ratio. Tactile activation aid/(B) = 0 to 0.9. Preferably 0 to 0.5 molar ratio.

Catalyst stabilizing aid VCA) = 0-200, preferably 0
~100 molar ratio.

Catalyst preparation is usually carried out using inert solvents. Examples of such solvents include aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as hexane, heptane, and cyclohexane, and halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene. Among them, aromatic hydrocarbons and halogenated aromatic hydrocarbons are preferred.

The catalyst preparation temperature is -80°C to 60°C, preferably -20°C.
~40°C.

The diminization reaction is usually carried out in an inert solvent as described above, but in some cases it can also be carried out in a liquefied lower α-olefin.

The catalyst concentration during the dihydrogenation reaction is selected from a range of about 10 −to mol/l IK as a nickel component in the reaction system. The double-wire reaction temperature is -80°C to 60°C, preferably -200°C to 40°C.

The reaction pressure is normal pressure or the equilibrium pressure generated by the reaction magnetism.

Examples of the lower α-olefin used in the present invention include ethylene, propylene, and 1-butene.

After the reaction is completed, the reaction is stopped according to the usual procedure, the catalyst is removed, and then the product can be obtained by rectification. The products were analyzed by gas chromatography;
Quantitated.

<Effects of the Invention> According to the present invention, equipment corrosion resistance, which was a problem with the conventional method.
Not only the heterogeneity of the catalyst in the reaction system is changed, but also the catalyst efficiency, selectivity, etc. -j- Same as above.

Furthermore, by changing the amount of fluorinated isopropanol used, the separation of double bond isomers in two animals can be controlled.
It also has the advantage of being able to do m.

<Example> The present invention will be described below in accordance with specific examples, but the present invention is not limited thereto. Nickel naphthenate 0.045
0.45 mmol of toluene solution and 0.045 mmol of tricyclohexylphosphine! A toluene bath containing 0.45 to 11 isoprene and 8.6 mmor (0,
86 ml) were added and mixed in this order, and then, under water cooling, 0.42 ml of a toluene solution containing 45 mmol of triethylaluminum Q was added and stirred. Next, under water cooling and stirring, 1.1,1,8,8.8-hexafluoroisopropanol (hereinafter abbreviated as HFIP) 1.85 mmo/
Add 185 txt of toluene solution containing the mixture and stir for an additional 15 minutes. After adding 8.5 ml of dry toluene to this catalyst solution, propylene was immediately added at a pressure of 4,000 ml, and the reaction was carried out at 20° C. for 80 minutes with stirring.

After the reaction, the reaction solution was sampled under pressure and analyzed by gas chromatography using n-pentane as a marker. The results are shown in Table 1. The reaction solution after purging unreacted propylene was clear, and no deposits were observed on the walls of the autoclave.

Example 2 The reaction was carried out in exactly the same manner as in Example 1, except that the amount of HFIP in Example 1 was changed to 0.675 mmo/. The obtained results are shown in 3-1.

Example 3 A 100 ml stainless steel autoclave was degassed and dried, then replaced with nitrogen, and 0.045 mmo of nickel naphthenate was placed in a stainless steel autoclave.
0.45 g/toluene solution containing r.

0.45 mmo of tricyclohexylphosphine/0.45 mmo of toluene and 1.8 mmo of isoprene!
(0.18 ml) were added and mixed in this order, and then 0.1 ml of triethylaluminum was added and mixed under water cooling. Stir 5 times. Next, under water cooling and stirring, tert-butyl chloride 0. 0 4 5
mmo! Toluene # liquid containing 0.45 crocodile! The mixture was stirred for 5 minutes, and then a toluene solution containing HFIPl, 35 mmO/1. Add 85 ml and stir for 15 minutes. Because of this catalyst, dry toluene is 8. After adding 5xtl, the pressure of propylene was kept at 44/d, and the reaction was carried out with stirring at 20°C for 80 minutes.

After the reaction was completed, it was analyzed in the same manner as in Example 1, and the results are shown in Table 2. The reaction solution was clear, and no deposits were observed on the walls of the autoclave.

Examples 11-12 A 100 ml stainless steel autoclave was degassed and dried, then replaced with nitrogen, and 0.0 ml of bis-triisopropylphosphine-nickel chloride was added. The toluene bath solution containing Olm mO/0. 5 ml 1 isoprene 0. 8 m
After adding 0.08 ml of toluene bath solution containing 9.2 mmoJ of triethylaluminum under water cooling. Add 5 ml and stir for 5 minutes.

Next, under water-cooled stirring, HFIP was mixed with the mixture shown in Table 4.
1 L/1 Stir for 5 minutes. After adding 8.511% of dry toluene to the resulting catalyst, 4% propylene was added immediately/d.
The pressure was maintained at 20°C, and the reaction was stirred for 80 minutes at 20°C. After the reaction was completed, analysis was performed according to Example 1, and the obtained results are shown in Table 4.

Example 21 To confirm the homogeneous solubility of the catalyst system, an accelerated test was conducted with increasing catalyst concentration as follows.

A 100 ml stainless steel autoclave was degassed and dried, then replaced with nitrogen a, and nickel naphthenate 0.1 mmo/
1 ml of chlorobenzene solution.

Tricyclohexylphosphine o, t mmo! Contains chlorobenzene FDK 11 Isoprene 8 mmo
1.1 (0.8 yst) was cooled and mixed in this order, and then 1.1 yst of triethylaluminum was added under water cooling. Add 1-l of On1mo/containing chlorobenzene solution and stir. Next, under water cooling, add 8 mmol of chlorobenzene solution containing 8 mmol of HF5P.
Add IIl and stir for 15 minutes. After adding 8.7 ml of dry chlorobenzene to this catalyst solution, 4 ml of propylene was added.
The pressure was maintained at Kf/d, and the mixture was stirred and reacted at 20° C. for 1 hour. After the reaction was completed, analysis was carried out in the same manner as in Example 1, and the obtained results are shown in Table 8. The reaction solution was clear, and only some precipitates were observed at the bottom of the reactor.

Comparative example 1 α, α in place of HFIP in Example 8.

115 mmo of α-trifluoroisopropanol! The reaction was carried out in the same manner as in Example 8 except for using the following. The results obtained are shown in Table-9.

Comparative Example 2 The following experiment was conducted according to Example 21 using trichlorophenol as a substitute for HFIP. A 100+/ stainless steel autoclave was degassed and dried, then replaced with nitrogen, and chlorobenzene f containing 0.1 mmol of nickel naphthenate was removed.
dH to Ig/.

Tricyclohexylphosphine 0. l mmo! Ltxls chlorobenzene solution containing isoprene
mmo/ (0,8 ml) and 0.5 mmo of water!
(9 μl) are added and blended in this order, and then, under water cooling, a chlorobenzene solution containing 1.0 mmoz of triethylaluminum is added once and stirred. Next, under water cooling, 2,4.6
- Add 8 ml of a chlorobenzene solution containing 8 mmol of dolichlorphenol and stir for 15 minutes. After adding 8.7 ml of dry chlorobenzene to this catalyst solution, the pressure of propylene was kept at 4 Kf/ci, and the mixture was stirred and reacted at 20° C. for 1 hour. After the reaction was completed, analysis was carried out in the same manner as in Example 1, and the obtained results are shown in Table 9. The reaction solution was opaque, and deposits were observed on the bottom of one reactor.

\、 \、 ゝ・、 ゝ＼ \、 ＼・、 ゛・、 ゛・、 Continued below Compensation Damage (self-inflicted) January//day, 1985 tentative (,) Commissioner of the Patent Office Kuro 1) Akio ■Display of incident 1986 Patent Application No. 0011G8 2. Name of the invention Dicomposition method for lower α-olefins 3. Person who makes corrections Relationship to the case Patent applicant 5-5, Kitahama 51-chome, Higashi-ku, Osaka Within Sumitomo Chemical Co., Ltd.

Patent Attorney (8597) Hikaru Moro;

Contact address: (06) 220-3404 Ushio, Subject of amendment (1) On page 14, lines 11-12 of the specification, “Catalyst...
It is... " is corrected to "Catalyst stabilizing aid/(B) = O to 0.9, preferably 0 to 0.5 molar ratio."

(2) Catalyst efficiency in Table 5 on page 24 (r)
30. Correct OJ to r30.0X103J.

that's all

Claims (1)

[Scope of Claims] When duplexing lower α-olefins, as a catalyst, (A) an organic salt or complex compound of nickel, (B) a trialkylaluminium, (C) general formula (I), (II) or ( III) PR^1R^2R^3 (I) P(NR^1_2)_3(II) P(OR^1)_3(III) (In the formula, R^1, R^2, and R^3 are each independent represents an alkyl, cycloalkyl or phenyl group), (D) General formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, (m and n represent integers satisfying 4≦m+n≦6) Using a catalyst consisting of four components of fluorinated isopropanol represented by
There are mathematical formulas, chemical formulas, tables, etc.▼(V) R^4R^5R^6CX(VI) (In the formula, X is a halogen atom, R^4, R^5, R^6
is a lower alkyl group, and n is a numerical value of 1 to 3. .