JPH0134A - Internal olefin production method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Industrial application field> The present invention relates to a method for producing internal olefins, and more particularly to a method for producing more stable internal olefins by isomerizing olefins in the presence of a specific catalyst. It is something.

<Problems that nine prior art inventions attempt to eliminate in 1F48>
Methods of isomerizing olefins to more stable internal olefins are well known.

However, generally known methods often involve decomposition of olefins, give unnecessary olefin polymers, and have many undesirable elements such as randomization (and suffer from economically disadvantageous limitations). ing.

As catalysts for such isomerization reactions, liquid bases such as mixtures of alkali metal hydroxides and aprotic organic solvents, alkali metal amides and amines, or organic alkali metals and aliphatic amines are known. However, methods using such liquid base reagents do not have sufficient catalytic activity, require large amounts of expensive reagents, and are difficult to separate and recover from the reaction mass.
This method not only requires a complicated separation and recovery process but also consumes a large amount of energy.

In addition, solid isomerization catalysts include catalysts in which alkali metals are dispersed in carriers with large surface species, such as activated carbon, silica gel, alumina, etc. (J, Am, Ch.
em, Soc, 82887 (1960)).

However, in such solid catalysts, the alkali metal itself is merely finely dispersed on a carrier, and when it comes into contact with air, it ignites and becomes deactivated, which poses a major problem in terms of operability and safety.

Also, the isomerization ability was unsatisfactory.

The present inventors have already developed a new catalyst using alumina, an alkali metal hydroxide, and an alkali metal as raw materials, as well as an alkali metal acting on hydrated alumina, as an efficient catalyst that does not have the problems of isomerization catalysts. In addition to discovering a catalyst, they also discovered that this product is safer and industrially acceptable as an isomerization catalyst because it does not pose the risk of ignition even in the air (Japanese Patent Publication No. 8274/1983, Publication No. 57-21878] This method is not necessarily completely satisfactory in terms of the use of an alkali metal as a raw material and the isomerization ability.

Furthermore, a method is also known in which a solid catalyst in which an alkali metal hydride is supported on a carrier is used in combination with ammonia or hydrazine (JP-A-58-121758; JP-A-58-121758;
9-184786 number t@).

However, since this method uses ammonia, hydrazine, etc. as an auxiliary agent, the auxiliary agent must be separated and recovered from the reaction mass, and not only does it require equipment for separation and recovery, but it also requires 4j7! n; also has the problem of survival.

The inventors of the present invention have conducted intensive studies to solve the problems of the above-mentioned known methods.
It was found that even when it is used alone, it exhibits a significantly high isomerization power, and after further various studies, the present invention was completed.

Means for Solving Problems> That is, the present invention isomerizes the double bonds of olefins to produce more stable internal olefins. 8 and Utt's alkali metal hydride in an inert gas atmosphere at 200 to 500°C.
The purpose of the present invention is to provide a method for producing an industrially extremely erodible internal olefin, which is characterized by using a solid base obtained by heating in a temperature range of .

As the hydrated alumina which is the raw material for the solid base in the present invention, hydrated alumina in the form of a mulch other than α-alumina is used.

Alumina is usually produced by firing aluminum hydroxide, but it is known that alumina in the form of a citrus tree, which takes on a quasi-stable structure depending on the firing temperature and firing time, and the amount of water contained in it, also exists. It is being In the present invention, such alumina is mainly used. In particular, hydrated alumina with a high surface area such as γ-11-1P-type is preferably used.

Furthermore, as the firing temperature increases, alumina eventually becomes α-
Switching to alumina, it is said that the sound reduction caused by heating of alumina will be eliminated. Although it is not so easy to measure the amount of water contained in alumina, α-
It can be expressed as Mu when heated until it turns into alumina.

The water content of the hydrated alumina used in the present invention is usually in the range of 1.2 to 10% by weight, preferably 2 to 7% by weight.

Further, examples of the alkali metal hydrides used in the present invention include sodium, potassium, and lithium hydrides belonging to Group 1 of the periodic table. There is no problem even if two or more of these alkali metal hydrides are used.

The amount of the alkali metal hydride used must exceed the molar amount of water in the hydrated alumina, and is preferably 1.01 to 2 times equivalent to the water.

When reacting an alkali metal hydride to hydrated alumina, a predetermined amount of the alkali metal hydride may be added at once, or an amount equivalent to the water content of the hydrated alumina may be added for sufficient reaction, and then the remaining alkali metal hydride may be added. You may also add chemicals.

In the latter case, the alkali metal hydride added to the light and the alkali metal hydride added later may be different.

These alkaline earth hydrides are generally easily available as powders or dispersions in an inert medium such as mineral oil, and if a dispersion in an inert medium is available, they may be used after separating the medium. However, it is also possible to separate the mixture by distillation or the like after using it together with the medium.

It is also possible to carry out a method in which an alkali metal is supported on hydrated alumina and then hydrogenated by acting on the alkali metal.

The catalyst used in the present invention is made by heating the above-mentioned hydrated alumina and alkali metal hydride at a specific temperature in an inert gas atmosphere and packing the mixture into a 1-Ail bag. ,・＼lium, argon, etc. are shown in 6.1j.

PI used in the present invention! i! The temperature at which the medium is prepared, that is, the temperature at which the hydrated alumina and the alkali metal hydride are heated, is extremely important and has a significant effect on the activity of the M medium. The catalyst preparation temperature is 200 to 500°C, more preferably 250 to 450°C. If a catalyst is prepared at such a temperature, a catalyst with extremely high activity never seen before can be obtained, and the desired reaction can be efficiently completed with a small amount of catalyst.

Heating time varies depending on the temperature conditions selected, but is usually 15
Minutes to 10 hours is sufficient.

In this way, the solid base used in the present invention is produced. The solid base is thought to generate new active species through the interaction of hydrated alumina and alkali metal hydride under heating, and has significantly higher activity than known catalysts, and is highly active when compared to known catalysts. The desired reaction can be completed without the need for any reagent at all, and even with a small amount.

The present invention uses such a solid base catalyst to isomerize olefins to more stable internal olefins,
Such raw material olefins include, for example, 1-butene, 1
-Pentene, 1-hexene, 1-heptene, 1-nonene, 1-decene, 2-methyl-1-butene, 8-methyl-
1-butene, 4-methyl-1-pentene, 8-methyl-
Chain compounds such as 1-pentene, 2-methyl-1-pentene, 2,8-dimethyl-1-butene, allylbenzene,
Aromatic compounds such as allyltoluene, bridged ring compounds such as 2-isopropenylnorbornane, 5-isopropenyl-2-norbornene, 5-vinyl-2-norbornene, 6-methyl-5-vinylnorbornene, methylenecyclopentane, methylenecyclohexane cyclic compounds such as 1.4
-pentadiene, 1゜5-hexadiene, 2,5-dimethyl-1,4-hexadiene, 2,5-dimethyl-1,
Terminal olefin compounds such as non-conjugated olefins such as 5-hexadiene, 4-methyl-2-pentene, 5-(2-
Examples include compounds that have a double bond other than the terminal and can be isomerized to a more stable position, such as (propenyl)-2-norbornene.

In producing internal olefins, the solid base catalyst used is usually 1/8000 to 1/20 of the weight of the raw material, and a weight of 1/2000 to 1/100 is sufficient. Regarding the isomerization temperature, there is no need to particularly heat the reaction as the reaction proceeds sufficiently at room temperature.
Depending on the purpose, it may be heated. Normally -80 to 120
It is preferably carried out at a temperature range of -10 to 100°C.

If necessary, the reaction can be carried out by diluting it with an inert medium, such as a hydrocarbon such as pentane, hexane, heptane, dodecane, etc., but since the desired product can be obtained just by separating the catalyst after the reaction, it is possible to carry out the reaction without a medium or by following the procedure. It is preferable to select the above-mentioned solvents used in the process.

The method of the present invention can be carried out either batchwise or continuously, and for isomerization, it is also effective to pre-treat the raw material with a desiccant such as alumina. In order to carry out isomerization more safely and reliably, it may be carried out under an inert gas atmosphere.

Isomerization reaction products and the like are analyzed by known methods such as gas chromatography, and easily separated from the catalyst by filtration, decantation, and the like.

<Effects of the Invention> In this way, an internal olefin that is isomerized to a more stable position, which is the object of the present invention, can be obtained, but according to the method of the present invention, an alkali metal hydride, which is easy to handle and easily obtained, can be used as a catalyst raw material. Moreover, the resulting catalyst has extremely high isomerization ability even without auxiliary agents such as ammonia or hydrazine.
Even with a small amount of catalyst, the olefin isomerization reaction can be completed extremely efficiently, and in addition, internal olefins can be obtained in high yield without producing by-products such as polymers. Furthermore, since the reaction can proceed safely without any danger of ignition, it is extremely advantageous as an industrial method for producing internal olefins.

<Examples> The present invention will be explained below according to specific examples, but the present invention is not limited to these examples.

Reference Example 1 γ-Alumina containing 2.2% by weight of water 25. Pour O2 into a 100 mJ flask, add sodium hydride (commercially available product, add hexane under nitrogen flow, filter,
After washing and removing mineral oil, use the dried one) 1.2
8F was added and the temperature was raised to 350°C with stirring, and the mixture was stirred at the same temperature for 1 hour. Next, let it cool to room temperature and solid salt-&25
．． I got 9f.

Reference Examples 2 to 9 The solid bases shown in Table 1 were obtained in the same manner as in Reference Example 1 except as shown in Table 1.

Example 1 0.189 g of the solid base prepared in Reference Example 1 was placed in a 200 ml flask under a nitrogen atmosphere, and 5-vinyl-2
-Norbornene [purity 99.9%] 65, Of was added and stirred at 15-20°C for 15 hours, and the reaction solution was measured by gas chromatography: 5-vinyl-2-norbornene (VNB) 0.8%. 5-ethylidene-2-norbornene (ENB) 99.6%. The catalyst was separated from the reaction solution to obtain 64.89% of the product.

Examples 2 to 6, Comparative Examples 1 to 8 An isomerization reaction was carried out in the same manner as in Example 1 except as shown in Table 2 using a 100 m flask under a violet atmosphere. The results are shown in Table-2.

Example 7 0.24 f of the solid base prepared in Reference Example 1 was placed in a 100 ml flask under a nitrogen atmosphere, and 5-isopropenyl-2-norbornene (89.9% endo type, 10.1% exo type) was added to the solid base prepared in Reference Example 1. Add 28.9r and heat at 15-20℃ for 20
After stirring for an hour, the reaction solution was analyzed by gas chromatography and found that endo-5-isopropenyl-2-norbornene <0.1%, exo-5-isopropenyl-2-
Norbornene was 0.8% and 5-isopropylidene-2-norbornene was 99.3%.

Example 8 A glass tube with an inner diameter of 5 mm and a length of 100 tubes was
Solid base prepared in Reference Example 1 under nitrogen atmosphere 0.95
Filled with F.

Pour cooling water at 15 to 20℃ into the outer tube, and
．． VNB (11111 degrees 99.
9%).

The composition of the reaction liquid flowing out from the bottom of the reactor was as follows.

Time (hr) VNB (%) ENB (%) 1
5 0, 8 9 9
．． 52 5 0, 8
9 9.58 5 0, 8
9 9.54 5 0, 8
9 9.5 Total outflow 152.1f1ENB
The average purity was 99.5%.

Example 9 0.25 f of the hedral base prepared in Reference Example 1 was placed in a 10 Oml flask under a nitrogen atmosphere, and 4-methyl-
1-Pentene28. Of, at 15-20℃, 1
It reacted for 6 hours.

After the reaction, the reaction solution was analyzed by gas chromatography and found that it contained 0.4% of 4-methyl-1-pentene, 9.2% of 4-methyl-2-pentene, and 90.2% of 2-methyl-2-pentene. Ta.

Example 10 0.24 t of the solid base prepared in Reference Example 5 was placed in a 20 Oml flask under a nitrogen atmosphere, and 4-methyl-
86.2F of 1-pentene was added and reacted at 15 to 20°C for 8 hours.

After the reaction, the reaction solution was analyzed by gas chromatography and found that it contained 0.8% of 4-methyl-1-pentene, 9.8% of 4-methyl-2-pentene, and 89.9% of 2-methyl-2-pentene. Ta.

Comparative Example 4 0.80 f of the solid base prepared in Reference Example 8 was placed in a 1 Q Oml flask under a nitrogen atmosphere, 6.42 g of 4-methyl-1-pentene was added thereto, and at 15 to 20°C, 48 g of the solid base prepared in Reference Example 8 was added.
Time reacted.

After the reaction, the reaction solution was analyzed by gas chromatography and found to be 89.8% of 4-methyl-1-pentene, 6.8% of 4-methyl-2-pentene, and 8.9'/G of 2-methyl-2-pentene. Met.

Comparative Example 5 Under a nitrogen atmosphere, solid bases o and aof prepared in Reference Example 9 were placed in a 1 U Oml flask, 15.89 g of 4-methyl-1-pentene was added thereto, and the mixture was heated at 15 to 20°C. , reacted for 48 hours.

After the reaction, the reaction solution was analyzed by gas chromatography, and it was found that 4-methyl-1-pentene was 0.6%, 4-methyl-2-pentene was 27.9%, and 2-methyl-2-pentene was 71.1%. Ta.

Hiraga Eneichi Seisho (self-proposal) May 72, 1986 2, Name of the invention, Process for producing internal olefins 3, Relationship to the case of the person making the amendment Patent applicant: 5-15 Kitahama, Higashi-ku, Osaka (209) ) Sumitomo Chemical Co., Ltd. Representative Hideo Mori 4, Agent 5-15 Kitahama, Higashi-ku, Osaka Contact address Ta, (06) 220-34045, Claims column of the specification to be amended and details of the invention Explanation column 6, Contents of amendment (1) The scope of claims is amended as shown in the attached sheet.

(2) In the 10th line of page 2 of the specification cylinder, the phrase "...etc., etc." should be corrected to "...etc....".

(3) Page 16, line 16, page 17, line 5, page 14
line and page 18, line 3, “...was...
” is corrected as [...was...j].

In producing more stable internal olefins by isomerizing olefins as claimed above, hydrated alumina and an alkali metal hydride in an amount exceeding the equivalent amount relative to the molar amount of water in the alumina are used as catalysts to inactivate olefins. 200 to 500° in gas atmosphere
A method for producing an internal olefin, characterized by using a solid base obtained by heating in a temperature range of C.

Claims (1)

[Claims] In producing a more stable internal olefin by isomerizing an internal olefin, hydrated alumina and an alkali metal hydride in an amount exceeding the equivalent amount relative to the molar amount of water in the alumina are used as a catalyst in an inert gas atmosphere at 200% ~50
A method for producing an internal olefin, characterized by using a solid base obtained by heating in a temperature range of 0°C.