JPS5820310B2 - Hydroesters - Google Patents

Description

Detailed Description of the Invention The present invention provides a method for separating and recovering activated cobalt from a reaction mixture in a method of hydroesterifying a cyclic olefin having 10 or more carbon atoms by reacting carbon monoxide and alcohol using a cobalt catalyst. It is related to.

In the reaction of hydroesterifying an olefin with carbon monoxide and alcohol using a cobalt catalyst, the cobalt catalyst becomes active cobalt such as dicobalt octacarbonyl and cobalt hydrocarbonyl during the reaction and dissolves into the system. is a liquid-phase homogeneous reaction.

Therefore, it is very difficult to separate and recover the catalyst from the product after the reaction is completed, which is an obstacle to industrialization.

Conventional methods for recovering cobalt catalysts include a method in which the product is heated to decompose cobalt carbonyl to produce metal cobalt, or a method in which the product is treated with a mineral acid or the like to produce a cobalt salt.

These methods not only have complicated processes and operations, but also have the disadvantage that, since activated cobalt is once returned to inactive cobalt, harsh conditions must be used again to convert it into activated cobalt when it is recycled and reused.

Recently, a method has been proposed in JP-A-47-11914 in which a hydrocarbon phase containing an ester and an alcohol phase containing activated cobalt are separated by mixing normally liquid hydrocarbons into a reaction mixture, and the catalyst is recovered and reused. There is.

This method has a simple recovery process compared to conventional technology,
Furthermore, since the recovered cobalt is in an active form, it is advantageous when it is recycled and reused.

However, this method requires a large amount of hydrocarbons to separate the two phases, and separation becomes difficult if a large amount of pyridine or the like is used as a co-catalyst to improve the selectivity of the reaction. It has the following drawbacks.

The present invention is a method for hydroesterifying a cyclic olefin having 10 or more carbon atoms by reacting carbon monoxide and alcohol using a cobalt catalyst, in which the reaction mixture is separated into two phases: a δ phase containing an ester and a phase containing a cobalt catalyst. The cobalt catalyst can be separated, recovered, and reused by adding sufficient water after the reaction, and since the catalyst recovered by this method maintains its active form, it is especially easy to reuse. The present invention has been developed based on the discovery that this is advantageous.

That is, the present invention uses a cobalt catalyst to reduce the number of carbon atoms to 10.
In the method of hydroesterifying a cyclic olefin by reacting carbon monoxide and alcohol, the hydroester is characterized by adding 1% by weight or more of water to the reaction mixture after the reaction to separate the cobalt catalyst. The present invention provides a method for recovering a catalyst in a chemical reaction.

The olefin in the present invention is a cyclic olefin having 10 or more carbon atoms, and includes 3a, 4,4a, 5,8°8a, 9,9
a-octahydro-4,9-methano-5,8-methano-
IH-benzo[b]indene, 3a, 4,4a, 5,6
,8,8a,9,9a-decahydro-4,9-methano-
5,8-methano-IH-benzo(b)indene, cto
Examples include commercially available cyclic olefin mixtures such as C12j C14jC16.

When using a cyclic olefin having 10 or more carbon atoms,
The catalyst can be separated efficiently with a small amount of water compared to chain olefins.

As the alcohol, primary, secondary, and tertiary alcohols having 1 to 10 carbon atoms can be used, but as the number of carbon atoms increases and the external waves increase, the reaction of the esterification reaction increases. Generally, primary and tertiary alcohols having 1 to 3 carbon atoms are most preferred because the speed decreases.

Specific examples include methanol, ethanol,
There is an isoproper tool.

The amount of alcohol used varies depending on whether or not a co-catalyst such as pyridine is used or the type of cyclic olefin having 10 or more carbon atoms to be used, but it is at least 1 mole, preferably 1.5 mole or more, based on the olefin. Preferably 2~
It is 30 times the molar amount.

If the amount of alcohol is too small, the catalyst cannot be separated sufficiently.

The type of cobalt catalyst is not particularly limited as long as it can form cobalt carbonyl under hydroesterification reaction conditions.

For example, mineral acid salts such as cobalt chloride, cobalt sulfate, and cobalt nitrate, organic acid salts such as cobalt acetate and cobalt naphthenate, cobalt oxide, cobalt metal, and dicobalt octacarbonyl are preferably used.

The cobalt catalyst concentration is usually 0.01 to 0.1 mole % based on the cyclic olefin having 10 or more carbon atoms.

In the hydroesterification reaction, a nitrogen-containing compound such as pyridine, quinoline, β-picoline, or γ-picoline is usually used as a cocatalyst to suppress the by-product of aldehyde. Catalysts can be efficiently separated and recovered regardless of their presence or absence.

In addition, when using the above-mentioned pyridine, etc., the amount used varies depending on the cyclic olefin having 10 or more carbon atoms, but
It is usually 2 to 60 times mole relative to cobalt.

After the hydroesterification reaction, the system becomes homogeneous, but by cooling the reaction mixture to below 60°C, adding water, stirring well, and leaving it to stand, the ester layer mainly containing unreacted olefin and cobalt are separated. It can be separated into two layers: a catalyst and an alcohol layer containing water.

When using a co-catalyst such as pyridine, the co-catalyst is distributed to both layers in various proportions depending on the type and conditions.

The optimum amount of water to be added is influenced by the type and amount of ester to be produced, the type and amount of alcohol, whether or not a co-catalyst is used, etc., but is usually 1% by weight or more of the reaction mixture, preferably 1 to 5% by weight.
00% by weight, more preferably 1 to 50% by weight.

If the amount of water is less than 1% by weight based on the reaction mixture, the catalyst cannot be efficiently separated.

According to the method of the present invention, the catalyst can be selectively transferred to the water-containing layer, and the catalyst can be recovered very efficiently.

The layer containing the catalyst may be an upper layer or a lower layer depending on the reaction recipe.

The catalyst-containing layer separated from the ester by the method of the present invention remains active when handled without coming into contact with process raw air, and is immediately used as a catalyst for the hydroesterification reaction without undergoing a reactivation step. It can be reused as

In this case, if the catalyst is kept under carbon monoxide pressure, decomposition of active cobalt carbonyl can be prevented.

Incidentally, the reaction product in the present invention is useful as an intermediate raw material for synthetic rosin acid and the like.

Percentages in the following examples are by weight unless otherwise stated.

Comparative Example 1 20.6 g (0,124 mol) of 1-dodecene and 33 ml of methanol were placed in a 1001 rLl autoclave equipped with an induction stirrer.
m1 (0,806 mol), pyridine 6.4.9 (0,
081 mole), cobalt acetate 1.58 p (0,0063
3 mol) was added.

After the autoclave was sufficiently purged with nitrogen gas, it was filled with carbon monoxide gas at room temperature in an amount of g□ky/i.

Next, heat the autoclave to 165°C and stir.6.
The reaction took place for 5 hours.

After the reaction, the autoclave was cooled and unreacted carbon oxide gas was exhausted.

The reaction mixture obtained by the above method was then transferred to a container which had been sufficiently purged with nitrogen, being careful not to come into contact with air, and the reaction mixture was a homogeneous liquid.

5.0 ml of H2O was added to this reaction mixture, and when the mixture was stirred vigorously and allowed to stand, it was separated into two layers.

Both layers were separated and analyzed and the upper layer contained 21.3% cobalt of the total cobalt charge and 62% ester based on the 1-dobcent charge and 27% of the pyridine charge.

On the other hand, the lower layer is based on 78.7% of the cobalt charged in addition to water and methanol, and 9% based on the charged 1-dodecene.
% ester and 72.7% of the charged pyridine.

Example 1 3a in JOOrrLl autoclave with induction stirrer.

4.5,6,7,8,8a,9,9a-decahydro-4
,9-methano-5,8-methano-IH-benzo(b)indene 20.1 g (0,100 mol) methanol 12 m
1 (0,300 mol), pyridine 740. Og(0,50
6 mol) and 1.24 Fl (0,005 mol) of cobalt acetate were charged.

After sufficiently purging the autoclave with nitrogen gas, the carbon monoxide gas was heated to 90ky/cr? at room temperature. Filled with L.

Next, the autoclave was heated to 165℃ and heated to 6.5℃ while stirring.
Time reacted.

After the reaction, the autoclave was cooled and unreacted carbon oxide gas was exhausted.

The reaction mixture obtained by the above method was then transferred to a container which had been sufficiently purged with nitrogen, being careful not to come into contact with air, and the reaction mixture was a homogeneous liquid.

8.1 rrtl of H2O was added to this reaction mixture, stirred vigorously and allowed to stand. The upper layer contained 96.8% of the total cobalt charged in addition to water and methanol, and 5 rrtl based on the charged olefin. % ester and 93.0% of the charged pyridine.

The bottom layer, on the other hand, contained 3.2% of the total cobalt charge, and 32% ester based on the olefin charge, and 7% of the pyridine charge.

Example 5 3a in 100ml autoclave with induction stirrer.

4.4a,5,8,8a,9,9a-octahydro-4
, 9-methano-5,8-methano-IH-benzo(b)indene 15 g (0,075 mol), methanol 6 ml (
0.15 mol), 15 g (0.19 mol) of pyridine, and 1.30 g (0.0037 mol) of dicobalt octacarbonyl were charged.

After the autoclave was sufficiently purged with nitrogen gas, it was filled with carbon monoxide gas at 90 kg/ffl at room temperature.

Next, the autoclave was heated to 135° C. (the pressure at this time was 120 ky/cIiL), and the reaction was allowed to proceed for 2 hours with stirring.

After the reaction, the autoclave was cooled and unreacted carbon oxide gas was exhausted.

The reaction mixture obtained by the above method was then transferred to a container which had been sufficiently purged with nitrogen, being careful not to come into contact with air, and the reaction mixture was a homogeneous liquid.

10 yd of H2O was added to the reaction mixture, stirred vigorously and allowed to stand, which then separated into two layers.

When both layers were taken out and analyzed separately, the upper layer contained, in addition to water and methanol, 87.0% of the total cobalt charged, 24% ester based on the charged olefin, and 89% of the charged pyridine). It was.

The lower layer, on the other hand, contained 13.0% cobalt of the total cobalt charge and 56% ester based on the olefin charge and 11% of the pyridine charge.

Claims (1)

[Claims] 1 In a method of hydroesterifying a cyclic olefin having 10 or more carbon atoms by reacting carbon monoxide and alcohol using a cobalt catalyst, the cobalt catalyst is added by adding 1% by weight or more of water to the reaction mixture after the reaction. A catalyst recovery method in a hydroesterification reaction characterized by separation.