JP2649068B2 - Metathesis catalyst for olefins and method of using the same - Google Patents

Description

The present invention relates to a highly active metathesis catalyst and a method for using the same.

<Prior Art> The metathesis reaction is generally the same as the metathesis reaction. For example, metathesis of an olefin can be represented by the following reaction formulas (I) and (II).

2R ¹ R ² C = CR ³ R ⁴ R ¹ R ² C = CR ¹ R ² + R ³ R ⁴ C = CR ^3R R ⁴ {(I) aAB + bCDcAA + dBB + eCC + fDD + gAD + hAC + iBC + jBD}
(II) (wherein RRC =, A, B, C and D represent alkylidene groups.) Metathesis was reported by Banks and Bailey in 1964 under the name olefin disproportionation reaction. Since then, various industrial processes have been industrialized. Conventionally, catalysts used for metathesis have been developed including heterogeneous systems, such as tungsten,
Compounds of molybdenum and rhenium, specifically WCl ₆ / LiBu,
MoCl ₂ (NO) ₂ py / Al ₂ (CH ₃ ) ₃ Cl ₃ (py indicates pyridine), WCl ₆ / SnBu ₄ , Re ₂ O ₇ ReO _{3 and the} like have been developed. In fact, it is limited to compounds of tungsten, molybdenum and rhenium, and rare earth metals
XCl ₄ (X represents titanium, zirconium and hafnium) catalysts are not known at all.

<Problems to be Solved by the Invention> An object of the present invention is to provide a metathesis catalyst for olefins that exhibits high activity and high selectivity for all metathesis reactions.

Another object of the present invention is to provide a method for using a metathesis catalyst for olefins which exhibits particularly excellent high activity and high selectivity for olefins.

<Means for Solving the Problems> According to the present invention, metathesis for olefins containing a salt of a metal selected from one or more of the group consisting of titanium, zirconium and hafnium and an activated rare earth metal. A catalyst is provided.

Further, according to the present invention, a metathesis catalyst containing a salt of a metal selected from one or more of the group consisting of titanium, zirconium and hafnium and an activated rare earth metal is heated under reduced pressure to activate the metathesis catalyst. A method for using a metathesis catalyst for olefins, wherein the metathesis catalyst is brought into contact with the olefin in a state where the olefin is brought into contact, and the olefin is subjected to a metathesis reaction.

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

The metathesis catalyst of the present invention is characterized by containing, as essential components, a salt of a metal selected from one or more of the group consisting of titanium, zirconium and hafnium and an activated rare earth metal.

The oxidation number of a metal selected from one or more of the group consisting of titanium, zirconium and hafnium used in the present invention is not particularly limited, but is preferably trivalent or tetravalent.

As the salt used in the present invention, for example, a halide salt, a complex salt and the like can be preferably mentioned, and specifically,
Preferable examples include salts of fluorine, chlorine, bromine and iodine, and complex salts such as alkoxides and acetylacetone.

In the present invention, in order to prepare a salt of a metal selected from one or more of the group consisting of titanium, zirconium and hafnium, for example, a salt such as a halogen element is formed on the metal at a high temperature. The components may be passed through. Specifically, in the case of preparing titanium (IV) chloride, it can be prepared by a known method such as synthesizing a mixture of titanium oxide (IV) and carbon with hot chlorine.

In the present invention, the rare earth metal is not particularly limited as long as it is activated, but samarium (Sm), ytterbium (Yb), europium (Eu) and the like can be preferably used. As a method for activating the rare earth metal, for example, after reducing the pressure in the reaction system to about 10 ⁻⁶ Torr, a sufficiently dehydrated and purified organic solvent such as tetrahydrofuran, cyclohexane, and benzene is applied to the inner wall of the reaction tube at −196 ° C.
Charged in a state of cooling and solidification to a degree, a rare earth metal vapor is vapor-dispersed and dispersed thereon, and then the reaction system is returned to room temperature and activated by a known method such as removing excess organic solvent. it can.

In the present invention, the metathesis catalyst containing a salt of a metal selected from one or more of the group consisting of titanium, zirconium and hafnium and an activated rare earth metal includes Sm-TiCl ₄ , Sm-TiBr ₄ , Sm-TiI ₄ , Sm-Ti
_{(0C 3 H7) 4, Sm} -ZrCl 4, Sm-ZrBr 4, Sm-ZrI 4, Sm-HfCl 4,
_{Sm-HfBr 4, Sm-HfI} 4 Yb-TiCl 4, Yb-TiBr 4, Yb-TiI 4, Yb
−Ti (0C ₃ H ₇ ) ₄ , Yb−ZrCl ₄ , Yb−ZrBr ₄ , Yb−ZrI ₄ , Yb−Hf
Cl ₄ , Yb-HfBr ₄ , Yb-HfI _{4 and the} like can be preferably mentioned.

To prepare the metathesis catalyst of the present invention, for example, one of the group consisting of titanium, zirconium and fhafnium is used.
A salt of a metal selected from the group consisting of two or more species and the activated rare earth metal is reacted with an organic solvent such as tetrahydrofuran or cyclohexane at a temperature of 20 to 60 ° C. for 3 to 10 minutes.
It can be prepared by using a method of reacting for an hour and removing the organic solvent. At this time, the content ratio of the metal salt and the activated rare earth metal is preferably 0.1 to 1 mmol, more preferably 0.4 to 0.6 mmol, for 1 g of the activated rare earth metal. It is desirable.

The substance that can be subjected to the metathesis reaction using the metathesis catalyst of the present invention is not particularly limited, and is effective in all metathesis reactions.

Next, a method of using the metathesis catalyst of the present invention to cause a metathesis reaction of an olefin will be described.

In the present invention, the metathesis catalyst containing a salt of a metal selected from one or more of the group consisting of titanium, zirconium and hafnium and an activated rare earth metal is, for example, 10 ^-4 to 10 ^-6 Torr. Decompress to the range, 200 ~ 300 ℃
For 2 to 3 hours, and preferably 1 to 5 g of the activated metathesis catalyst per 1 mol of olefin is reacted at a reaction temperature of 100 to 200 ° C. and a pressure of 30 to 10
By bringing the olefin into contact with the olefin within the range of 0 torr, there is almost no side reaction, and the olefin can be subjected to a metathesis reaction. The olefin that can be subjected to the metathesis reaction is not particularly limited, but, for example, propylene, butene, isobutene, pentene, chain olefins such as hexene, cyclopentene,
Cyclic olefins such as cyclooctene and cyclododecene,
Conjugated dienes such as butadiene and isoprene can be effectively metathesized.

<Effect of the Invention> By using the metathesis catalyst of the present invention, high activity and high selectivity are exhibited in the olefin metathesis reaction. Further, in the present invention, in particular, an olefin can be subjected to a metathesis reaction with high activity and high selectivity.

<Examples> Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 30 ml of sufficiently dehydrated and purified tetrahydrofuran was charged into a vacuum evaporation apparatus in which the pressure in the reaction system was reduced to 10 ⁻⁶ Torr, and −196.
After cooling and solidifying at 1 ° C., 1 g of samarium vapor was evaporated and dispersed in the reaction system while keeping the temperature at −196 ° C. to obtain 1 g of samarium particles. Next, 1 g of the obtained samarium particles and 0.52 mmol of tetrachlorotitanium were added to 50 parts of tetrahydrofuran.
The mixture was placed in Schlenk together with the ml, and stirred at room temperature of 25 ° C. for 3 hours. Then, the inside of the reaction system was adjusted to 10 ⁻⁴ Torr, and tetrahydrofuran was removed to obtain about 1 g of the target metathesis catalyst. When the obtained compound was subjected to elemental analysis by plasma emission spectrometry (ICP), it was Sm-TiCl _4. The metathesis activity of the obtained compound was measured by reacting with propylene at 100 ° C. and 90 Torr. Table 1 shows the results.

Example 2 The heating exhaust temperature of samarium and tetrachlorotitanium was
A target metathesis catalyst was obtained in the same manner as in Example 1 except that the temperature was changed to 250 ° C., and the metathesis activity was measured. Table 1 shows the results.

Example 3 A target metathesis catalyst was obtained and the metathesis characteristics were measured in the same manner as in Example 1 except that 0.58 mmol of tetrachlorotitanium and a heating and exhausting temperature of 200 ° C. were obtained. Table 1 shows the results.

Example 4 A target metathesis catalyst was obtained in the same manner as in Example 3 except that the amount of tetrachlorotitanium was changed to 0.65 mmol, and the metathesis activity was measured in the same manner as in Example 1. Table 1 shows the results.

Example 5 A metathesis catalyst was obtained in the same manner as in Example 1 except that 1 g of ytterbium vapor was used instead of 1 g of samarium vapor, 0.39 mmol of tetrachlorotitanium was used, and the heating and exhausting temperature was 200 ° C. The resulting metathesis catalyst was a Yb-TiCl ₄ was subjected to elemental analysis by plasma emission spectrometry (ICP). The metathesis activity of the obtained metathesis catalyst was measured in the same manner as in Example 1. Table 1 shows the results.

Example 6 A target metathesis catalyst was obtained in the same manner as in Example 5 except that the amount of tetrachlorotitanium was changed to 0.60 mmol, and the metathesis activity was measured. Table 1 shows the results.

Comparative example 1 Except not using tetrachlorotitanium, it processed similarly to Example 2 and activated samarium. Next, Example 1
The metathesis activity was measured under the same conditions as described above. Table 1 shows the results.

Example 7 0.3 g of Sm-TiCl ₄ obtained in Example 1 was put into a U-shaped reaction tube, the pressure inside the reactor was reduced to 10 ⁻⁵ Torr,
After heating for one hour, 0.3 g of the Sm-TiCl ₄ and 29 ml of propylene (9
0 torr) was reacted for 3 hours at a heating / exhausting temperature of 100 ° C. using a closed-volume closed-circulation system having a constant volume.
l and 0.015 mmol of 2-butene were obtained. FIG. 1 shows the relationship between the amount of ethylene and 2-butene produced during the reaction and time.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the production amount of ethylene and 2-butene and time when propylene is subjected to a metathesis reaction using Sm-TiCl ₄ as a metathesis catalyst of the present invention.

Claims (2)

(57) [Claims] 1. A metathesis catalyst for olefins comprising a salt of a metal selected from one or more of the group consisting of titanium, zirconium and hafnium and an activated rare earth metal. 2. An olefin metathesis catalyst comprising a salt of a metal selected from one or more of the group consisting of titanium, zirconium and hafnium and an activated rare earth metal is heated under reduced pressure to activate A method for using a metathesis catalyst for olefins, wherein the metathesis catalyst is brought into contact with an olefin in the state where the metathesis catalyst is brought into contact with the olefin.