JPH0296549A - Hydroformylation of unsaturated fatty acid compound - Google Patents

Abstract

PURPOSE:To obtain hydroformylated compounds in a low concentration of rhodium at a moderate rate in a high yield by specifying the content of polyenes in the above-mentioned raw material and the amount of the above-mentioned catalyst used in hydroformylation of an unsaturated fatty acid compound in the presence of a rhodium catalyst. CONSTITUTION:In hydroformylation of a monounsaturated fatty acid compound (monoene compound) containing unsaturated fatty acid compounds (polyene compound) having >=2 carbon-carbon double bonds in the molecule by reaction with hydrogen and carbon monooxide in the presence of a rhodium catalyst, the above-mentioned polyene compounds are used in an amount of <=6.0wt.%, preferably 0.005-5.5wt.% based on the total amount of the monoene and polyene compounds and the above-mentioned catalyst is used in an amount of (1.4X10<-5>)-(1.9X10<-2>)wt.%, preferably (1.4X10<-4>)-(1.7X10<-2>)wt.% as a converted value into rhodium atom based on the total amount of the monoene and the polyene compounds to produce the objective hydroformylated compounds at a moderate rate in a very high yield in such a low-rhodium concentration that the condition is industrially advantageous.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a method for producing a formylated product having seven more carbon atoms (hereinafter referred to as "formylated compound") by hydroformylation in the presence of a λ metal. The formyl compound is easily hydrogenated by a conventional method to be induced into the hydroxymethyl compound. this is,
It is a compound useful as an intermediate raw material for surfactants, etc.

[Conventional technology]

A method of producing an aldehyde or its hydrogenated alcohol by reacting an olefinic compound with a water gas in the presence of a catalyst is well known as a hydroformylation method. As a catalyst, a carbonyl complex of cobalt or rhodium is usually used. Among them, the use of rhodium carbonyl generally provides high activity and high selectivity for aldehydes.

Among olefinic compounds, especially unsubstituted olefins, the activity of rhodium catalysts is high, and industrially sufficient reaction results can be achieved even under low rhodium concentration conditions.

On the other hand, in the hydroformylation of substituted olefins, various results can be obtained depending on the type of substituent. For example, regarding the hydroformylation of unsaturated fatty acid compounds, a method for hydroformylating unsaturated fatty acid compounds in the presence of supported rhodium and tertiary phosphine is disclosed in US Patent No. 3,71.
7p! It is described in the specification of No. 7. However, in this method, 0.02 to 0
, 4 L by weight of rhodium was used to obtain suitable reaction rates and yields.

[Problem to be solved by the invention]

However, since rhodium is an extremely expensive metal, it is industrially important to reduce its usage, and the challenge is to perform hydroformylation at an appropriate rate and in high yield under conditions of low rhodium concentration. there were.

[Means to solve the problem]

In view of the above-mentioned state of the prior art, the present inventors have conducted intensive studies to find a method for producing formyl compounds from unsaturated fatty acid compounds at low rhodium concentrations and in high yields. By using an unsaturated fatty acid compound with regulated hydroformylation as a raw material for the hydroformylation reaction and using conditions with a previously unknown low rhodium concentration, we have demonstrated that formyl compounds can be obtained at an appropriate rate and in extremely high yields. This discovery led to the completion of the present invention.

That is, the present invention provides a monounsaturated fatty acid compound (hereinafter referred to as "monoene compound") containing an unsaturated fatty acid compound (hereinafter referred to as "polyene compound") having λ or more carbon-carbon double bonds in the molecule. In the method of hydroformylation by reacting with hydrogen and carbon monoxide in the presence of a rhodium catalyst, the amount of the polyene compound is 6.0% by weight or less based on the total amount of the monoene compound and the polyene compound, and the rhodium catalyst The concentration is rhodium atom equivalent value, based on the total amount of monoene body and polyene body /, 4L × 70-5 ~ /, Ri × 1
The gist of this invention is a hydroformyl method for unsaturated fatty acid compounds, which is characterized in that the amount of unsaturated fatty acid compounds is 0''% by weight.

The present invention will be explained in detail below.

The unsaturated fatty acid compounds targeted by the method of the present invention are highly unsaturated fatty acids and unsaturated fatty acid esters that are widely produced as components of animal fats and vegetable oils. As the unsaturated fatty acid ester, an ester of an unsaturated fatty acid and a monohydric alcohol is usually used. Specific examples of unsaturated fatty acid compounds include monounsaturated fatty acids with a carbon number of 1 and 1, such as palmitoleic acid and oleic acid, which exist in relatively large amounts in nature, and palmitol 1/methyl inoate,
Examples include esterified products of monounsaturated fatty acids with carbon numbers/o and i, such as methyl oleate, ethyl oleate, and butyl oleate.

By the way, it is industrially difficult to obtain these monounsaturated fatty acid compounds, that is, monoene compounds, with high purity.
It is usually obtained as a mixture of fatty acid compounds having a carbon number distribution and different degrees of unsaturation. The present invention thus targets the hydroformylation of monounsaturated fatty acid compounds (monoene compounds) containing unsaturated fatty acid compounds (polyene compounds) having λ or more carbon-carbon double bonds in the molecule. be.

Therefore, the method of the present invention is widely applicable to the hydroformylation of monoenes containing polyenes, but preferably monoenes, ie, mixtures of fatty acid compounds containing 70% by weight or more of monounsaturated fatty acid compounds, are used.

In the method of the present invention, when hydroformylating a monounsaturated fatty acid compound (monoene compound) containing an unsaturated fatty acid compound (polyene compound) having λ or more carbon-carbon double bonds in the molecule, The amount of the polyene body is 6.0% by weight or less based on the total amount of the monoene body and the polyene body,
Preferably o, o o j-r, weight%, more preferably o, oi-hiro weight ratio, particularly preferably 0.05 to 3
It is important to use something that has a weight rating.

If the content of the polyene body exceeds 6.0% by weight, as will be described later, the formyl body cannot be produced at a low rhodium concentration, at a good reaction rate, and in a high yield. Furthermore, as will be described later, the content of polyenes can be reduced by selective hydrogenation, etc., but under conditions of excessive hydrogenation, monoenes are consumed, resulting in poor efficiency and economical efficiency. Because of this tendency, it is usually permissible to include a small amount of polyene in consideration of economic efficiency.

The method for bringing the content of the polyene into the specified range is not particularly limited, but any known method for selectively hydrogenating the polyene into a monoene may be employed.

Specifically, for example, Ni/diatomaceous earth, Cu-Cr/S
i A hydrogenation catalyst selected from O,, Pd/σ, Pd/Al, 01, etc. is added at a concentration of 0.0/-70% by weight based on the total amount of unsaturated fatty acid compounds (total amount of polyenes and monoenes). % by weight, hydrogen pressure from normal pressure to ioow/Cr/lG,
A monounsaturated fatty acid compound having a desired polyene content can be obtained by reacting for several hours at a temperature of room temperature to 200°C and separating the catalyst by a known method such as distillation or filtration. However, there are limits to the selective hydrogenation of polyenes, which are taken into account from the efficiency and economics of hydrogenation. In the method of the present invention, from the viewpoint of the efficiency of the hydroformylation reaction and the economical efficiency of the hydrogenation reaction, the inclusion of a certain amount of polyene is usually allowed as described above, and sufficient results can thereby be obtained. .

As the rhodium catalyst used in the hydroformylation reaction of the present invention, any known rhodium-containing hydroformylation catalyst can be used, but among them, suitable rhodium compounds include RhH(Co)(PPh8)s, Rh
(OAc)(Co)(PPh*)t, (Rh(O
Ac ) COD L (Rh (OAc) (COL)
9 Rhodium complexes such as (AC-acetyl group, C0D=/, j-cyclooctadiene); organic acid salts of rhodium such as rhodium acetate; inorganic acid salts of rhodium such as rhodium nitrate and rhodium sulfate; or rhodium/carbon Examples include supported rhodium such as. The amount of the rhodium compound to be used is such that the concentration in the reaction zone is 7.4'
x 1o-2 weight ratio preferably 6. guxio-'～6.
It is selected within an industrially advantageous low rhodium concentration range of 7 x 10-2 weight factors. If the rhodium concentration is less than the above range, a sufficient reaction rate cannot be obtained. Furthermore, if the rhodium concentration is higher than the above range, the effects of the present invention obtained by setting the polyene content within the specific range cannot be obtained.

In the method of the present invention, a ligand used in a general rhodium-catalyzed reaction can be used in combination, if desired, taking into consideration the selectivity of the hydroformylation reaction and the catalytic activity. Specifically, tertiary phosphine such as triphenylphosphine, tritolylphosphine, tris(methoxyphenyl)phosphine, bis(2-cyanoethyl)phenylphosphine, tributylphosphine, tricyclohequinylphosphine, tribenzylphosphine; trifinyl Examples include tertiary phosphites such as phosphite and tridecyl phosphite; tertiary amines such as tributylamine and triphenylamine.

The amount of the ligand to be used is not particularly limited and may be used arbitrarily to obtain a desired result, but usually,
It is selected from the range of about /-j 00 mol, preferably /-200 mol per mol of rhodium atom.

In carrying out the hydroformylation reaction, it is not essential to use a reaction solvent, but if necessary, a solvent inert to the hydroformylation reaction can be present. Specific examples of preferred solvents include aromatic hydrocarbon compounds such as toluene, xylene, and dodecylbenzene, ketones such as acetone, diethyl ketone, and methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, ethyl acetate, and di-n.
-Esters such as octyl phthalate can be mentioned.

Regarding the reaction conditions, the reaction temperature is usually room temperature to 20D°C, preferably! The reaction pressure is usually normal pressure to 300 atm, preferably 200 atm.
It's out of the atmospheric pressure range.

The molar ratio of hydrogen and carbon monoxide (H2/Co) is usually
/0//~t7'to, preferably ///~&/
Selected from the range /.

The hydroformylation reaction according to the method of the present invention can be carried out industrially in either a continuous method or a batch method in a stirred reactor or a bubble column reactor. The formed formyl compound can be separated from the reaction mixture by a known method such as distillation.

Rhodium can be recovered by a known method from the residual liquid containing the catalyst from which the formyl compound has been separated. or,
At least a portion of the residual liquid may be recycled to the hydroformylation reaction step to reuse the catalyst.

〔Example〕

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Raw materials a)/! 0ral and / % P d / A l
20s powder catalyst/, 30? After charging the mixture into a stainless steel induction stirring autoclave having an internal volume of 200 ytl, the autoclave was sealed. Furthermore, 1014 nitrogen gas
After repeating the operation of pressurizing to /dG and releasing to normal pressure three times, the temperature was raised to ioooc. After reaching 100°C,
Hydrogen gas! The hydrogenation reaction was carried out without intermittent feeding at 9/cr/l (:).During the course of the hydrogenation reaction, the contents were sampled and analyzed by gas chromatography to monitor the reaction.After the hydrogenation reaction was completed, The catalyst was separated using a 0.0, gμ membrane filter.

The above hydrogenation reaction was carried out for an arbitrary period of time to prepare raw material mixtures having different polyene contents (raw materials A and C in Table 1).

Further, raw material a was distilled on a clear day and then subjected to the same hydrogenation reaction as described above to prepare raw material mixtures having different polyene contents (raw materials d and C in Table 1).

Furthermore, commercially available methyl linoleate was added to raw material d to create a raw material mixture with different polyene content (raw materials f and g in Table 1).
) was prepared.

Example-/~6 Raw material b (Example-2) obtained in Reference Example-/, Raw material C (Example-7 and Raw material C (Example-3), Raw material f (Example-≠)) or raw material g (Example-j) 60 penalties, m
-Xylene j ml! , and a methanol solution of rhodium acetate (7.371% my/?-methanol as rhodium metal) in an amount to give a predetermined rhodium concentration in a stainless steel vertically stirred autoclave with an internal volume of 200.1 cm under a nitrogen atmosphere. After charging, the autoclave was sealed. Furthermore, nitrogen gas / o kg/c6. After press-fitting to G, repeating the operation of releasing to normal pressure three times, t3o
The temperature was raised to ℃. Immediately after reaching 730℃, the total pressure becomes t7o.
Water gas (H2/co
=') was injected under pressure to start the reaction. The reaction was continued at this reaction temperature for the reaction time shown in Table 1. The water gas consumed by the reaction is replenished from the pressure accumulator through a constant pressure device.
The reaction pressure was constantly maintained at t 7 H/cr/IG. After the reaction, a sample was taken out and the product concentration was measured by gas chromatography analysis. The results are shown in Table 2.

Comparative Example-1-≠ Commercially available oleic acid methyl ester (raw material a in Table-7) A
The procedure was the same as in Example 7, except that Orttl was used instead of raw material 7 and the reaction was carried out under the conditions shown in Table 2. Table 2 shows the results of gas chromatography analysis after the reaction.

Example-7 Reference Example-/Raw material dlrOml, m-xylene! vrl, a methanol solution of rhodium acetate in an amount to give the Rh concentration shown in Table 3 and triphenylphosphine in the amount shown in Table 3 were placed in a stainless steel autoclave with an internal capacity of 200 m1, and the reaction time was set to /,! The reaction was carried out in the same manner as in Example-/, except for changing the time. Table 3 shows the results of gas chromatography analysis after the reaction.

〔Effect of the invention〕

According to the method of the present invention, a formyl compound can be obtained in high yield from a monounsaturated fatty acid compound containing a polyene compound at a low rhodium concentration.

Claims (1)

[Claims] (1) Monounsaturated fatty acid compounds (hereinafter referred to as "monoene compounds") containing unsaturated fatty acid compounds having two or more carbon-carbon double bonds in the molecule (hereinafter referred to as "polyene compounds")
) is reacted with hydrogen and carbon monoxide in the presence of a rhodium catalyst to hydroformylate, wherein the amount of the polyene is 6.0% by weight or less based on the total amount of the monoene and the polyene. , the concentration of the rhodium catalyst is 1.4 x 10^-^5 to 1.9 x 10^-5 relative to the total amount of the monoene body and polyene body, in terms of rhodium atoms.
A method for hydroformylating an unsaturated fatty acid compound, characterized in that the amount is 2% by weight.