JPS62226939A - Production of aldehyde - Google Patents

Abstract

PURPOSE:To improve the thermal stability of a catalyst and to increase the yield of aldehyde in the hydroformylation of an olefin compound having vinyl group at a terminal in the presence of a rhodium complex compound, by adding a specific organic phosphorus compound to the reaction system. CONSTITUTION:An aldehyde is produced by the hydroformylation of an olefin compound having vinyl group at a terminal in an organic solvent in the presence of a rhodium complex compound (catalyst). The reaction is carried out in the presence of one or more organic phosphorus compounds selected from PRO(OH) H and (RO)2POH (R is alkyl or aryl) optionally in combination with a tertiary phosphine compound. The thermal stability of the catalyst can be improved, the lowering of olefin conversion caused by the repeated use of the catalyst can be prevented and undesirable isomerization reaction and hydrogenation reaction of olefin can be suppressed. Accordingly, the objective compound can be produced in high selectivity and yield with prolonged catalytic life.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing aldehydes, and more specifically, the present invention relates to a method for producing aldehydes. In this process, the thermal stability of the catalyst system is improved to prevent the olefin conversion rate from decreasing even when the catalyst is repeatedly used, and the isomerization reaction of the olefin is suppressed, thereby increasing the desired yield of aldehyde. The present invention relates to a method for producing an aldehyde that can increase the

[Prior Art] Conventionally, when producing aldehydes by the hydroformylation reaction of olefins, it has been common to use cobalt complex compounds and rhodium complex compounds as catalysts, but when this rhodium complex compound is used alone, the reaction The conditions had to be high temperature and high pressure, which was disadvantageous in that it led to an increase in manufacturing costs.

Therefore, an attempt has been made to stabilize the catalyst system by adding a large amount of a tertiary phosphine compound together with the above-mentioned catalyst to the hydroformylation reaction system, and it has been confirmed that this allows the reaction to proceed at low temperature and low pressure. ing.

By the way, in this hydroformylation reaction, in order to distill and separate the target aldehyde from the reaction product mixture, the higher the olefin is, the more severe the conditions must be to carry out the reaction under reduced pressure and at a higher temperature. . Therefore, as the catalyst is repeatedly reused, i.e., as the vacuum distillation operation at high temperature described above is repeated, thermal degradation of the catalyst occurs and the catalyst is deactivated, resulting in a decrease in olefin conversion and a decrease in aldehyde conversion. Inconveniences occur such as a decrease in the yield of olefins and an acceleration of the isomerization reaction of olefins.

[Problems to be solved by the invention] As described above, in the conventional method for producing aldehyde,
There were problems such as a decrease in olefin conversion rate and an increase in isomerization reactions due to the low thermal stability of the catalyst.

The present invention solves the conventional problems and increases the conversion rate of olefins by improving the thermal stability of the catalyst.
Moreover, it is an object of the present invention to provide a method for producing an aldehyde that can suppress the isomerization reaction of olefins, thereby obtaining the desired aldehyde in high yield, and in which the life of the catalyst is long.

[Means for Solving the Problems] As a result of extensive research to achieve the above object, the present inventors discovered that the present inventors have developed a method using a rhodium complex compound that has been used in the past as a catalyst to be present in the reaction system, and a rhodium complex compound that has a specific structure. The present invention was completed after confirming that when used in combination with an organic phosphorus compound, the thermal stability of the rhodium complex compound as a catalyst at high temperatures is improved and excellent effects can be obtained.

That is, the present invention is a method for producing an aldehyde by hydroformylating an olefinic compound having a vinyl group at the end in an organic solvent in the presence of a rhodium complex compound, the reaction system containing the following formula: % Organic phosphorus represented by the formula %() and the following formula (RO)2PO)I -...- (IN (in formulas CI) and (II), R represents an alkyl group or an aryl group) It is characterized by the presence of at least one kind of compounds.

[Specific Description] The method for producing an aldehyde of the present invention can be applied to any process for producing an aldehyde by hydroformylating an olefinic compound having a terminal vinyl group.

First, the olefinic compound having a terminal vinyl group, which is a starting material, is not particularly limited, and includes, for example, aliphatic hydrocarbon olefins having 20 or less carbon atoms, specifically ethylene, propylene, -butene, 1
- pentene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1,11-dodecadiene, or dimers or dimers thereof; and allyl alcohol, acrolein acetal, vinyl acetate, styrene, Examples include olefins such as alkyl vinyl ethers.

In addition, the rhodium complex compound used as a catalyst is not limited to, for example, HRh (Co) [
Preferred examples include P barrel) 3] 3.

Next, in the method of the present invention, the organic phosphorus compound used together with the rhodium complex compound has the above formula CI
) and (IT). In these formulas, R is not particularly limited as long as it is an alkyl group or an aryl group;
It is preferably a hydrocarbon group of 0 or less, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, etc. aliphatic saturated hydrocarbon group;
Examples include substituted or unsubstituted aromatic hydrocarbon groups such as phenyl, tolyl, ethyl phenyl, and xylyl groups, and alicyclic hydrocarbon groups such as dichlorohexyl and methylcyclohexyl groups. Among them, phenyl group,
Substituted or unsubstituted aromatic hydrocarbon groups such as tolyl, ethylphenyl, and xylyl are preferred.

Furthermore, in the method of the present invention, a tertiary phosphine compound can be used, if necessary, in addition to the above-mentioned catalyst and organic phosphorus compound. This tertiary phosphine compound is represented by the formula: PR'R"R"°, where R', R" and R"" may be the same or different, such as an aryl group, An aryloxy group or an alkoxy group is preferable.Specific examples of particularly preferable tertiary phosphine compounds include triphenylphosphine, tritolylphosphine, trinaphthylphosphine, triphenylphosphite, trimethylphosphite, and triethylphosphine. , tributyl phosphite, etc.

Next, the steps for producing an aldehyde of the present invention will be explained step by step.

First, starting materials such as an olefinic compound, a rhodium complex compound, an organic phosphorus compound, and optionally a tertiary phosphine compound are dissolved in an organic solvent and charged into a reaction vessel. The organic solvent to be used is not particularly limited, but includes, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and dodecylbenzene; alicyclic hydrocarbons such as cyclohexane; dibutyl ether, ethylene glycol dimethyl ether , diethylene glycol ethyl ether, triethylene glycol dimethyl ether, and tetrahydrofuran; esters such as diethyl phthalate and dioctyl phthalate are preferred. Note that the generated aldehyde can be used as it is as a solvent.

Further, the concentration of the catalyst, that is, the rhodium complex compound at this time, is preferably 0.1 to 10 mmol/su,
The amount of the organic phosphorus compound of formula CI) and/or formula (II) to be used is preferably set to at least 1 mol in total per 1 mol of the rhodium complex compound.

Thereafter, a mixed gas of CO and H2 is introduced into the container to carry out a hydroformylation reaction.

The reaction conditions at this time are a temperature of 10 to 200'C, further 60 to 120'C, and a mixed gas pressure of 1 to 100 kg/
cm2. Furthermore, 5 to 30 kg/cm2. It is preferable to set the reaction time to 0.5 to 5 hours. Then, at the end of the reaction, the desired aldehyde is obtained by distilling the reaction product from the reaction solution under reduced pressure.

Furthermore, in the method of the present invention, since the thermal stability of the catalyst is extremely good, an olefinic compound as a starting material is charged into the reaction solution after the reaction product is distilled off under reduced pressure, and the hydroformylation reaction is carried out again. It is possible to do this. Furthermore, the method of the present invention can be applied to either a batch method or a continuous method, and can industrially produce aldehydes with high efficiency.

[Example] Example 1 In a glass autoclave with an internal volume of 67 cc and equipped with a stirrer,
Catalyst, RhH(Co)(PPh3)3(Ph:
A mixed gas of H2 and co (H2 /CO molar ratio: 1).

Then, a mixed gas was introduced until the total concentration was 6 kg/cm2, and the reaction was carried out at 80°C for 120 minutes while stirring at 600 ppm. After the reaction was completed, the container was left to cool and depressurized, and the resulting yellow reaction liquid was analyzed by gas chromatography. The results are shown in Table 1.

Example 2 Instead of PhPH(0)OH as an organic phosphorus compound, (I
I-Bud)2 POH (Bu: butyl group) 0.25
The reaction was carried out in the same manner as in Example 1 above, except that mmol was used. The yellow reaction solution obtained was analyzed by gas chromatography and the results are shown in Table 1.

Example 3 Instead of PhPH(0)OH as an organic phosphorus compound, (P
The reaction was carried out in the same manner as in Example 1 except that 0.09 mmol of hO)2POH was added and the reaction time was 70 minutes, and the resulting orange reaction solution was analyzed by gas chromatography. The results were analyzed and shown in Table 1.

Comparative Example 1 30.05 mmol of RhH(Co)(PPh3) as a catalyst and 25 mmol of 1-octene as an olefin were dissolved in 50 mmol of toluene, charged into a glass autoclave, and mixed so that the total pressure was 6 kg/cm2. Introducing gas (H2/Co molar ratio = 1) and heating at 80'O
The reaction was carried out for 40 minutes. The color of the solution gradually changed to brown, and after the reaction was completed, it became a deep reddish brown. The reaction solution obtained was analyzed by gas chromatography, and the results are shown in Table 1.

Table 1 Example 4 In a glass autoclave with an internal volume of 67 cc and equipped with a stirrer,
As a catalyst, 30.15 mmol of RhH(Co)(PPh3), as an organic phosphorus compound PhPH(0)OHO,
75 mmol of triphenylphosphine as a tertiary phosphine and 40 mmol of 1-tetradecene as an olefin were dissolved in 150 mmol of toluene, and the inside of the container was filled with a mixed gas of H2 and CO (
Sufficient substitution was made with H2/CO molar ratio = 1).

Then, a mixed gas was introduced until the total pressure reached 6 kg/cm2, and the reaction was carried out at 80° C. for 180 minutes while stirring at 600 rpm. After the reaction is completed, the reaction product and a portion of the solvent are removed from the reaction solution by vacuum distillation, and 1-tetradecene 32 is newly added to the remaining reaction solution.
Millimoles were added and reacted for 3 hours under the same conditions as above.

Incidentally, the vacuum distillation was carried out at a pressure of 3 to 5 mmHg and by raising the bath temperature to a maximum of 140°C. Such addition of 1-tetradecene and re-reaction were repeated a total of seven times, resulting in eight hydroformylation reactions including the first reaction. After each reaction was completed, the reaction solution was analyzed by gas chromatography to determine the olefin conversion rate, aldehyde selectivity, and hydrogenation/isomerization selectivity, and the results are shown in Table 2.

Table 2 Comparative Example 2 The reaction was repeated in the same manner as in Example 4 above except that PhPH(0)OH was not used.
Shown in the table.

Table 3 [Effects of the Invention] As is clear from the above explanation, according to the method for producing aldehydes of the present invention, undesirable olefin isomerization reactions and hydrogenation reactions are suppressed, and aldehydes can be produced with high selectivity. can be obtained (Table 1), and because the thermal stability of the catalyst is improved, the catalyst can be used repeatedly without reducing the olefin conversion rate (Table 2).
Therefore, its industrial value is extremely large.

Procedural amendment June 18, 1986

Claims (2)

[Claims] (1) A method for producing an aldehyde by hydroformylating an olefinic compound having a vinyl group at the end in an organic solvent in the presence of a rhodium complex compound, the reaction system containing the following formula: RPO(OH) H・・・・・・・・・(I) and,
The following formula (RO)_2POH・・・・・・・・・(II) (However,
In formulas (I) and (II), R represents an alkyl group or an aryl group. (2) The manufacturing method according to claim 1, wherein a tertiary phosphine compound is further present in the reaction system.