JPS60126243A - Production of aliphatic carboxylic acid - Google Patents

Abstract

PURPOSE:To produce the titled compound in high yield, by oxidizing a cyclic and/or an acrylic aliphatic olefin with a peroxide, and oxidatively cleaving the resultant oxidation product with molecular oxygen in the presence of a heavy metal and a bromine compound and if necessary a chlorine compound. CONSTITUTION:A cyclic and/or an acrylic aliphatic olefin having at least one unsaturated bond in the carbon chain is made to react with a peroxide, and the resultant oxidation product is subjected to the oxidative cleavage with molecular oxygen in the presence of a catalyst composed of (A) a heavy metal, e.g. metal having an atomic number of 23-32, 39-51 or 57-84, especially Co, Mn, Ce, etc. and (B) a bromine compound, and if necessary (C) a chlorine compound to obtain the titled compound useful as a raw material of plasticizer, etc. from a raw material available easily at a low cost, in high yield. The process is economical in industrial view point because the addition of expensive peracetic acid, etc. is not necessary. The above components B and C are especially preferably hydride, ammonium salt, sodium salt, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing aliphatic carboxylic acids by oxidative cleavage of cyclic and/or acyclic aliphatic olefins.

More specifically, cyclic and/or acyclic aliphatic olefins are oxidized by the action of a peroxide, and the resulting oxidation product is oxidatively cleaved with molecular oxygen in the presence of a specific catalyst to obtain high yields. The present invention relates to a method for producing aliphatic carboxylic acids at high yields.

Conventionally, ozone, nitric acid,
Methods using oxidizing agents such as permanganate are known. However, ozone and permanganate are expensive, and when cheap nitric acid is used, a large amount of polymer is produced and the yield is poor. Attempts have also been made to use hydrogen peroxide as an inexpensive oxidizing agent to replace these expensive oxidizing agents, to introduce a diol group adjacent to the double bond, and to air oxidize this in the presence of a cobalt salt catalyst. (JP-A-47-6014, JP-A-47-1970, JP-A-47-9018)
No. 49-135909, Japanese Patent Application Laid-Open No. 1972
-3815, JP-A-49-135908, etc.). However, this method has many problems in addition to the inability to selectively synthesize adjacent diols as intermediate raw materials, as well as the oxidative cleavage reaction itself. Generally, methods for introducing adjacent diol groups into unsaturated bonds include a method in which hydrogen peroxide and water are reacted in the presence of an acid catalyst to form adjacent diols in one step, and a method in which an epoxide is first formed and then hydrolyzed. Are known. However, in the former, the epoxide as a reaction intermediate is unstable and has poor reaction selectivity because it coexists with an acid, and reacts again with the adjacent diol as a product to produce an ether as a by-product. On the other hand, the latter requires many steps (or requires special treatment such as heating epoxide with water and a large amount of fatty acid salt at high temperature (Japanese Patent Laid-Open No. 57-57459, ) 3). Additionally, this reaction of cleaving adjacent diol groups requires a long induction period, consumes expensive peracetic acid, ketones, aldehydes, etc., and requires extreme purification of raw materials and solvents in order to carry out continuous reactions. There are a number of disadvantages, such as the need for measures such as the need to keep the oxidation reaction in check and the need to limit its supply so as not to stop the oxidation reaction. As mentioned above, none of the known methods is satisfactory as a method for producing aliphatic carboxylic acids by oxidative cleavage of cyclic and/or acyclic aliphatic olefins.

Dicarboxylic acids obtained from cycloaliphatic olefins are important as plasticizers and raw materials for polyesters, and monocarboxylic acids obtained from acyclic aliphatic olefins are important as raw materials for lubricants, etc. Since aliphatic olefins can be easily and inexpensively produced as petrochemical products, it is more advantageous to oxidatively cleave cyclic and/or acyclic aliphatic olefins to produce aliphatic carboxylic acids. There is a need for a method for manufacturing it.

The present inventors have conducted intensive studies to find an excellent method for producing aliphatic carboxylic acids by subjecting cyclic and/or acyclic aliphatic olefins to oxidative cleavage using an inexpensive oxidizing agent or air. As a result, by oxidizing the oxidation product obtained by reacting a peroxide with a cyclic and/or acyclic aliphatic olefin with molecular oxygen in the presence of a specific catalyst, the desired product can be obtained in high yield. The present inventors have discovered that an aliphatic carboxylic acid can be obtained, and have completed the present invention.

That is, the present invention uses an oxidation product obtained by reacting a peroxide with a cyclic and/or acyclic aliphatic olefin having at least one unsaturated bond in its carbon chain, and oxidizing it with heavy metals and bromine. It is characterized by oxidative cleavage using molecular oxygen in the presence of a catalyst consisting of a compound or a heavy metal, a bromine compound, and a chlorine compound.

The cyclic and/or acyclic aliphatic olefin used as a raw material in the present invention is an olefin having at least one carbon-carbon double bond. Specifically, cyclopentene, cyclohexene, cyclooctene, dicyclopentadiene, 1-hexene, 3-hexene, 1-heptene, 1
-Octene, 2-octene, 4-octene, 1-nonene, 1-decene, 5-decene, 6-decene, 1-dodecene, 1-tetradecene, 7-tetradecene, 1-hexadecene, 8-hexadecene, 1 Examples include -octadecene and 9-octadecene.

The oxygen-containing groups introduced by the action of a peroxide on the double bonds of these olefins include adjacent diol groups, epoxy groups, hydroxyl groups and ether groups, hydroxyl groups and nitrite groups, ester groups and ether groups, etc. Various methods can be considered for introducing these oxygen-containing groups. For example, in the presence of a catalyst such as formic acid, mineral acid-carboxylic acid, tungstic acid, molybdic acid, vanadate acid, etc., or a catalyst using a combination thereof, hydrogen peroxide is applied in a solvent or non-solvent system, pertungstic acid, A method using inorganic peroxides such as permolybdic acid and permanganic acid, a method using organic peroxides such as performic acid, peracetic acid, perbenzoic acid, and perchlorobenzoic acid, cumene hydroperoxide, t-butyl hydroperoxide A method of reacting organic peroxides such as molybdenum, vanadium, or tungsten salts in the presence of a catalyst, or adding aldehydes such as acetaldehyde or benzaldehyde to supply molecular oxygen in the presence of a trace amount of a cobalt salt catalyst. A method of reacting while producing an organic peracid can be adopted. However, the method is not limited to the above method as long as it achieves the objective.

Catalysts suitable for the present invention consist of a heavy metal and a bromine compound or a heavy metal, a bromine compound and a chlorine compound.

As heavy metals, atomic numbers 23-32.39-51.5
7 to 84 are exemplified. Among these, cobalt, manganese, cerium, etc. are particularly preferred. These heavy metals may be in the form of simple elements, oxides, salts, or complexes. On the other hand, bromine compounds consist of the bromine molecule, its acid,
It may be a salt, an oxyacid salt, or an organic bromine compound.

Particularly preferred are hydrogen bromide, ammonium bromide, sodium bromide, cobalt bromide, manganese bromide, cerium bromide, nickel bromide, tetrabromoethane, tribromoethane, and the like. As for the chlorine compound, those having the same form as the above-mentioned bromine compound can be used. The term "same form" used here includes not only compounds with the same form, such as simple molecules, oxides, salts, and complexes, but also compounds represented by a molecular formula in which the bromine atom is simply replaced with a chlorine atom. and as noted below.
"same form" has the above meaning.

Examples of suitable catalysts include powdered cobalt metal and ammonium bromide, cobalt bromide, cobalt acetate and ammonium bromide, cobalt acetate and sodium bromide, cobalt acetate and potassium bromide, cobalt acetate and hydrogen bromide, acetic acid. These include cobalt and tetrabromoethane, manganese bromide, manganese acetate and hydrogen bromide, manganese acetate and ammonium bromide, manganese acetate and tetrabromoethane, etc. These bromine compounds can partially replace chlorine compounds of the same type. Further, a catalyst comprising a combination of two or more heavy metals and a bromine compound, or a combination of two or more heavy metals, a bromine compound, and a chlorine compound is advantageous in that it eliminates the induction period and has a high reaction rate. In this case, the heavy metals are preferably a combination of two or more of cobalt, manganese, cerium, and nickel. For example, cobalt bromide and manganese bromide, cobalt bromide and manganese acetate, cobalt acetate and manganese bromide,
Manganese acetate and cobalt acetate and ammonium bromide, manganese acetate and cobalt acetate and hydrogen bromide, cobalt bromide and cerium acetate, cobalt acetate and cerium bromide, manganese bromide and cerium acetate, cobalt bromide and nickel acetate and bromide ammonium, cobalt acetate and manganese acetate and cerium acetate and ammonium bromide, cobalt naphthenate and manganese nanthenate and tetrabromoethane, cobalt acetylacetate and manganese acetylacetate and hydrogen bromide,
Examples include cobalt acetate, manganese acetate and sodium bromide, cobalt acetate, manganese acetate, cerium acetate and sodium bromide, cobalt naphthenate, manganese acetate and potassium bromide. Further, a part of these bromine compounds can be replaced with a chlorine compound of the same type. Note that the present invention is not limited to the above-mentioned examples.

The amount of heavy metals is 0.05 metal equivalent concentration per liter of raw material.
~105'/n is suitable. If it is less than 0.055'/#, a sufficient reaction rate cannot be obtained, and if it is more than 10'i/1, there will be disadvantages such as an increase in the expense required for the catalyst and an increase in side reactants. The appropriate amount of the bromine compound or the total amount of the bromine compound and chlorine compound used is 0.1 to 100 equivalents per heavy metal atom in terms of bromine atom. If the amount is less than 0.1 equivalent, a sufficient reaction rate cannot be obtained, and if it is more than 100 equivalents, the product may be contaminated with bromine or chlorine, and the cost required for the catalyst may increase, which is not preferable.

If the bromine compound or chlorine compound is accompanied by exhaust gas and exits the reaction system during the reaction, the reaction rate will be reduced, so it is preferable to carry out the reaction while adding the bromine compound or chlorine compound as appropriate. In this case, the additional amount may be 1%/h or less based on the oxidation raw material in terms of bromine atoms.

A reaction solvent is not necessarily required, but when the melting point of the raw material is high or when a solvent is used to remove the heat of reaction, an organic compound that is inert to oxidation or relatively stable under the reaction conditions is used. For example, a saturated monocarboxylic acid having about 2 to 10 carbon atoms is preferred, and acetic acid is particularly suitable.

As the molecular oxygen used as the oxidizing agent, pure oxygen or industrial exhaust gas can be used, but the present invention is not limited to these, and any gas containing oxygen may be used, and from an industrial perspective, normal air is most suitable.

The reaction pressure is a total reaction pressure of 0 to 100 klj/clr.
G, preferably 2 to 40 kg/dG, and the oxygen partial pressure is preferably 0.1 to 10 kg/Cd. Furthermore, from a safety perspective, the oxygen concentration in the exhaust gas from the reactor must be 8.
It is desirable to operate so that it is less than % by volume.

The reaction temperature is 60-200°C, preferably 80-140°C.
It is °C. If the temperature is lower than 60°C, the reaction rate will be low, while if it exceeds 200°C, the solvent and product will be unfavorably decomposed into carbon dioxide.

The concentration of water in the reaction solution is maintained at 15% or less (preferably. The produced water can be removed from the system along with the exhaust gas during the reaction, but in particular, a means for removing water may be used. It is also possible to react as is without taking steps.Water accumulates when the solvent is used repeatedly, but the concentration of water at the end of the reaction is 1
It can be used without removing water until it reaches 596.

The method of the present invention is generally carried out as follows.

A peroxide such as hydrogen peroxide or an organic peracid is applied to a raw material, cyclic and/or acyclic aliphatic olefin, in a reactor equipped with a stirrer and equipped with a gas inlet and a gas outlet. The product containing an oxygen-containing group obtained by the process, a catalyst, and optionally a solvent are charged, replaced with air or pressurized, and heated to a predetermined temperature. During this temperature rising period, stirring and gas blowing are not necessarily required. Oxygen absorption depends on the type and concentration of the catalyst, the type and composition of the raw materials, but is generally 60 to 100%.
Starting from °C. Air is introduced when oxygen absorption begins, and the reaction takes place while maintaining a predetermined oxygen partial pressure.

The exhaust gas may be cooled with water, and the resulting condensate may be returned to the reactor or taken out of the system.

The bromine compound can be reacted without being added after being charged at the start of the reaction, but if a higher degree of reaction per reactor is desired, it is preferable to add the bromine compound little by little as the reaction progresses. In this case, liquids such as tetrabromoethane are left as they are, and solids such as ammonium bromide are dissolved in water or a solvent and are fed continuously or intermittently using a pump. After reacting for a predetermined time, it is cooled and the reactant is taken out. First, after distilling off the solvent used, the desired product can be obtained by distillation if the product is a monocarboxylic acid, or by distillation if the product is camidicarboxylic acid, or by using water etc. It can also be obtained by recrystallization.

In addition to the above-mentioned stirring type reactor, any closed container capable of mixing gas and liquid, such as a bubble column 1 artificial waterfall type, can be used. Furthermore, the reaction method is not limited to a batch method.

Continuous reactions are also possible. Raw materials, catalyst, and if necessary, a solvent are continuously supplied to the reactor, and while oxygen or oxygen-containing gas is blown into the reactor, the reaction product is withdrawn at a fixed residence time. At this time, there is no need to limit the feeding rate of the raw materials or solvent in order to maintain the raw materials. Even when part of the bromine compound is replaced with a chlorine compound, the reaction can be carried out in exactly the same manner.

In the conventional method described above, since oxidative cleavage was impossible except for adjacent diol groups, it was necessary to selectively diolize carbon-carbon double bonds in the raw material. In contrast, the method of the present invention uses a specific catalyst to introduce not only adjacent diol groups but also oxygen-containing substituents such as epoxy groups, hydroxyl groups and esters, hydroxyl groups and ether groups, and ester groups and ether groups. Carbon-carbon double bonds can be selectively oxidized and cleaved. Therefore, by very easily obtaining an intermediate material that undergoes oxidative cleavage with molecular oxygen, it is possible to obtain the desired aliphatic carboxylic acid at a very high yield (A) for aliphatic olefins.

Furthermore, the oxidative cleavage method of the present invention does not require the addition of expensive peracetic acid, ketones, aldehydes, or the like. Furthermore, when performing continuous reactions, there is no need to particularly purify the raw materials or solvents, and there are no special measures such as restricting their supply so that the reaction does not stop. It has industrial advantages.

Examples will be shown below and specifically explained in detail.

Example 1 1-decene 160) acetic acid 100 & concentrated sulfuric acid 0.47
Add 60% hydrogen peroxide to this at 65-70"C.
5' was added dropwise over a period of 1 hour, and the reaction was further allowed to proceed at this temperature for 5 hours. After adding 0.22 kg of sodium hydroxide to the reaction mixture, acetic acid, water, etc. were distilled off under reduced pressure, and the mixture was washed with water. The obtained oily substance had an iodine value of 2, an adjacent hydroxyl value of 140, and an adjacent hydroxyl value of 293 after saponification. Next, the above oily substance is oxidized in air.

A titanium autoclave with an internal volume of 500 resistant. ln a enemy trh l n
n W fM, cobalt oxide (CoBr ・6H,O) 0
．． 669 and arsenic acid? 7 Crab, y [Mn (OOCC
H3) 2.4H2o)o, 5o2 were charged, air was introduced, and the reaction pressure was 25'kQ/cAG (oxygen partial pressure 2kl).
j/Cd) while heating and stirring. Oxygen absorption started at 80'C. The reaction temperature is 100°C. One hour and two hours after the reaction, 1 tttt of a 20% aqueous ammonium bromide solution was added. After a total of 3 hours of reaction, almost no oxygen absorption was observed. After the reaction product was cooled, it was distilled under reduced pressure to remove acetic acid, and further distilled under reduced pressure to obtain 71 g of distillate.

As a result of analysis by gas chromatography, this distillate contained 6% by weight of short chain fatty acids having 4 to 7 carbon atoms, 6% by weight of caprylic acid, and 88% by weight of pelargonic acid. The yield of this pelargonic acid corresponds to 85 mol % based on the raw material 1-decene.

Example 2 88% formic acid 39) was added to 123 g of cyclohexene, and 6
1027 of 6096 hydrogen peroxide was added dropwise at 5 to 70'C over 1 hour, and the mixture was reacted at 80'C for 6 hours.

Formic acid, water, etc. are distilled off from the reaction product under reduced pressure to obtain an oily substance of 20
I got 29. The obtained oily substance had an iodine value of 4, an adjacent hydroxyl value of 407, and an adjacent hydroxyl value of 658 after saponification.

Next, the above oily substance 1002 was placed in the same reactor as in Example 1.
, acetic acid 1ooy, cobalt acetate [co(OOCCH)・
4Ho] 0.502 Cerium acetate (111) 0.635
' and 0.81% of 47% hydrobromic acid at 100°C.
While blowing air, the reaction pressure was 25 kV/cAGc.
The reaction was carried out at an oxygen partial pressure of 2 kQ/ca). After 2 hours of reaction,
When 2 ml of 2096 ammonium bromide aqueous solution was added and the reaction was continued for an additional 2 hours, almost no oxygen absorption was observed. After acetic acid and water were distilled off from the reaction mixture, 138 pieces of solid distillate were obtained by distillation under reduced pressure. As a result of analysis by gas chromatography, the composition of this distillate was 3% by weight of succinic acid, 10% by weight of glutaric acid, and 87% by weight of adipic acid.
% by weight. The yield of adipic acid corresponds to 82 mol% based on the raw material cyclohexene.

Example 3 ■-Decene 160V was operated in the same manner as in Example 1, and the obtained oily substance 100F was placed in a titanium autoclave,
Acetic acid 1005', cobalt bromide [coBr-6HO]
0.33', cobalt acetate (Co (OOCCH3)2
・4 H2O) 0.25 S', mangaf acetate [
Mn (OOCCH) 4HO) 0.50 El and concentrated hydrochloric acid 0.17 P are added. The reaction was carried out at 100"C while blowing air at a reaction pressure of 25 kq/ctA G (oxygen partial pressure 2 kq/cd). One hour and two hours after starting the reaction, a 10% ammonium chloride aqueous solution was added to I
After adding Nt in portions and reacting for 13 hours, almost no oxygen absorption was observed. After distilling off the acetic acid, distillate 707 was obtained by distillation under reduced pressure. As a result of analysis by gas chromatography, this distillate has 4 to 7 carbon atoms.
6% by weight of short-chain fatty acids, 7% by weight of caprylic acid, and 87% by weight of pelargonic acid. The yield of this pelargonic acid is
This corresponds to 85 mol% based on 1-decene.

Comparative Example 1 1-decene 160v was operated in the same manner as in Example 1, and f211
．． e+1#-! I+41'NnM 1 f'l I'l
qilt4: M 1 n A u g! cobalt acid (
Co (OOCCH) Fist 4HOEO, 50! v, manganese acetate [Mn(OOCCH)・4HO) 0.50P was charged into the same autoclave as in Example 1, and while blowing air at 100'C, the reaction pressure was 25 kg/cA G (
The reaction was carried out for 3 hours at an oxygen partial pressure of 2 kq/crA). After the reaction was completed, acetic acid was distilled off and distilled under reduced pressure to obtain distillate 195'. As a result of analysis by gas chromatography, this distillate contained 7% by weight of short chain fatty acids having 4 to 7 carbon atoms, 19% by weight of caprylic acid, and 74% by weight of pelargonic acid.

The yield of this pelargonic acid is 2
This corresponds to 0 mol%.

As described above, when a known catalyst containing no bromine compound or chlorine compound is used, the yield of aliphatic carboxylic acid obtained is extremely low.

Procedural amendment angle (method) April 10, 1980 Director-General of the Patent Office Kazuo Wakasugi 1, Indication of case 1981 Patent In 112355
No. 52 No. 2, Name of the invention Process for producing aliphatic carboxylic acid 3, Relationship with the provincial case making the amendment Patent applicant address 13 Yoshishima Yairo-cho, Fushimi-ku, Kyoto-shi, Kyoto Prefecture? I ground 4, amendment order fJ March 7, 1980 (shipment date 1972)
(March 27, 9)

Claims (1)

[Claims] The oxidation product obtained by reacting a peroxide with a cyclic and/or acyclic aliphatic olefin having at least one unsaturated bond in its carbon chain is combined with a heavy metal and a bromine compound or with a heavy metal. A method for producing aliphatic carboxylic acids, characterized by oxidative cleavage with molecular oxygen in the presence of a catalyst consisting of a bromine compound and a chlorine compound.