DE2303925B2 - Process for the preparation of aliphatic dicarboxylic acids - Google Patents

Description

The present invention relates to a process for the preparation of aliphatic dicarboxylic acids by Ozonolysis of cycloolefins according to the preceding claim.

Dicarboxylic acids are used in the synthesis of polyester and polyamide resins and plasticizers for use.

In the FR-PS 13 91338 a process for the production of dicarboxylic acids by ozonolysis of cyclododecene in the solution lower monocarboxylic acids at 25 ° C, followed by Oxydationszersetzung of the ozonolysis products in the oxygen or air stream is described with gradually increasing temperature from 80 to 110 ⁰ C. Because the thermal oxidation decomposition of the ozonolysis products of the formula

OOH

(CHj) _n -CH

O — COR

where R is an alkyl radical and η is between 2 and 10, is carried out in lower monocarboxylic acids at elevated temperature, by-products are obtained as a result of the incorporation of oxygen into the aliphatic chain, decarbonylation of the aldehyde group and the formation of compression products. This complicates the process for producing the required quality acid. It is necessary to use complicated and expensive methods of cleaning. The yield of the end product in the known processes does not exceed 70% of theory.

FR-PS 1173 225 describes a process for the production of haloglutaric acids using H ₂ SO ₄ as the oxidation catalyst, while in the process according to the invention the ozonolysis products are oxidized on cation exchange resins to give aliphatic dicarboxylic acids. To remove the H2SO4, NH3 is used there, which in turn makes it necessary to _{remove the (NH 4} I ₂ SO _{4 produced by neutralization).}

US Pat. No. 3,466,302 describes the production of polycarboxylic acids from substituted alkylcyclohexanes by oxidizing the ozonolysis products with H ₂ O ₂ in the presence of H 2 SO 4.

The US-PS 28 33 786 also describes a process for the production of hydroxyglutaric acid, of their lactone and of haloglutaric acid.

The halogen-containing cyclopentanes are ozonized in solvents and the ozonides obtained with them an aqueous H2Or solution in the presence of a strong mineral acid oxidizes

The US-PS 29 62 528 describes a process for the production of halogen-containing glutaric acids. The halogen-containing cyclopentanes are ozonized in solvents and the ozonides obtained are oxidized with an aqueous H ₂ Or solution in the presence of a strong mineral acid at a pH of at most 2 in CH3COOH

GB-PS 7 72 410 is also not relevant. Here is a method of making aliphatic Dicarboxylic acids described in ozonization

is cyclic olefins with one or more double bonds to ozonides and in the hydrolysis of the same and oxidation with O ₂ or an or-containing gas in the presence of catalysts (KMnO ₄ , Cr ₂ O ₃ , Co ₂ O ₃ ). Various organic liquids can be used as solvents can be used in which the starting olefin and the ozonolysis product are soluble, in particular ethyl acetate

The GB-PS 9 65 510 describes a process for the preparation of «-ω-alkanedicarboxylic acid, which is in the Ozonization of cyclic olefins of the formula

CH

(CH,),

«= 4 to 10

CH

in solvents, preferably in propionic acid, with subsequent oxidative decomposition of the _{ozonization products. The oxidizing agent used is O 2} J-) with a low ozone content.

This literatu place is not for the following reasons relevant:

Monocarboxylic acids are proposed as solvents for ozonization, but in particular propionic acid, since this leads to a considerably higher yield than is the case with the other acids. The fundamental difference now lies in the fact that the oxidation in the GB-PS with O _{2 takes place} in the presence of O3 (the possible use of oxidation initiators, catalysts and catalysts is also indicated).

US Pat. No. 3,441,604 describes a process for the preparation of dicarboxylic acids by ozonolysis of cycloolefins in a solution of monocarboxylic acids with subsequent oxidation of the ozonolysis products, eg with air or O2 in the presence of 10 to 35% by weight H ₂ O.

The yield of dicarboxylic acid is 60 to 74% of theory and the degree of purity is at most 97 to 98 Wt%. This patent is not applicable for the following reasons:

In the process according to the invention, on the other hand, the ozonolysis products are oxidized with an aqueous H2O ₂ solution in the presence of acidic cation exchange resins as a catalyst, in particular cation exchangers, by polymerizing styrene and divinylbenzene with ion exchange groups SO3H (KU-2-8) and then thermally converted. This process for converting ozonolysis products leads to an increase in the yield and the degree of purity of the dicarboxylic acids.

The process according to the invention produces yields of approx. 89; it is also very simple and therefore economically interesting.

Cycloolefins are subjected to ozcnolysis between 20 and 40 ° C in lower monocarboxylic acids (ζ, Β. Acetic or propionic acid).

The ozonolysis products are 20 to 30% iger Treated aqueous hydrogen peroxide solution This further treatment of the reaction mixture obtained is carried out in two series-connected processes Reactors through.

In the first reactor an acidic cation exchange resin, e.g. B. K.U-2-8 or US ion exchange resin Amberlite 1 R120 (see the book by N. T. Poüanski "Katalis ionitamie, M, Chemie" pages 7,8,9,10,11,12

10 and 204, 206) is present, passed through the addition of hydrogen peroxide obtained after the reaction mixture between 30 and 60 ⁰ C with a Volumgeschwindigkeit 2-4 St '. The reaction mixture then enters the second reactor at a volume rate of 0.3 to 0.5 hours, where post-oxidation takes place at a temperature of 50 to 80 ° C. in the absence of a catalyst

The oxidation process of the ozonolysis products can be carried out using acetic acid and cyclododecene the following scheme can be shown:

1. CH ₃ COOH + H ₂ O ₂ * O

± CH ₃ CO ₃ H + H ₂ O OOH O

OH

OOH

OH

2. CH ₃ CO ₃ H -τ C (CH ₂ J ₁₀ -CH -

H OCOCH ₃

CH ₃ C-CO-CH- (Ch ₂ J ₁₀ CH 'CH ₃ COOH

OCOCH ₃

Il

Supreme Court

OCOCH ₃

Upon contact of the reaction mixture with the acidic cation exchange resin, e.g. B. KU-2-8, is im in the first stage the peracetic acid is formed and part of the ozonolysis product (about 20 to 30%) is oxidized; in the The second stage is the homogeneous oxidation of the ozonolysis product with the peracetic acid in the absence of the acid catalyst.

30th After oxidation, the ozonolysis products pass from the second reactor to the thermal one Decomposition.

This reaction takes place in the absence of a catalyst at a temperature between 90 and 110 ° C carried out for 2 to 4 hours and proceeds according to the following scheme:

HO

OOH

C (CH ₂ J ₁₀ -CH-O

OCOCHj

OH O

I Il

-C- (CH ₂ J ₁₀ -C + CH ₃ COOH O OH

Thus, succinic acid is obtained from cyclododeca- -ine triene and cyclooctadiene, suberic acid from cyclooctene, 1,10-decanedicarboxylic acid from cyclododecene.

The isolation of the dicarboxylic acids from the decomposition products, which are a dicarboxylic acid solution in aqueous monocarboxylic acid, and their 4; Purification is carried out depending on the properties of the final product obtained.

The main part of monocarboxylic acid (95 to 97%) together with water is between 40 and 50 ° C at a residual pressure of 50 to 100 torr.

The rectification conditions are chosen depending on the properties of the monocarboxylic acid.

The remaining portion of the above acid (3 to 5%) at the same residual pressure and the same temperature as an azeotropic mixture after the addition of v, the corresponding solvent (n-heptane in the use of acetic acid as the reaction medium and ethylbenzene with the use of the propionic acid) aborted.

The monocarboxylic acid / solvent ratio is <, n carries 1: 6.

After completion of azeotropic distillation drying succinic and Korksäurekristalle traces of solvent between 70 and 8O ⁰ C for 2 to 3 hours. (T ₁

To get the UO-decanedicarboxylic acid from aqueous To isolate monocarboxylic acid solution, one derives from the oxidation reactor coming mixture of Products in a heat exchanger operated at 100 ° C, in which the oxidized products of the Cycloolefin ozonolysis decomposes, then cools the solution to 15 to 20 ° C, cleans the precipitated with water Crystals of 1,10-decanedicarboxylic acid of traces of monocarboxylic acid and dried at a temperature of 70 to 80 ° C for 3 hours.

The yield of dicarboxylic acids is 98 to 99% of theory.

With the help of gas-liquid chromatography certain degree of purity of the acids obtained by the process according to the invention is approximately 99.5%.

The following process conditions are preferred:

The ozonolysis of cycloolefins is at a temperature of 25 to 30 ° C with ozonated air (Ozone content of 1.5 to 2% by weight) in 99.2 to 99.6% acetic acid. The use of higher molecular weight monocarboxylic acids is impractical because of their relatively high cost and lower usability because solutions of ozonolysis products of the compounds mentioned are more difficult to separate in these acids.

The oxidation of ozonolysis products must be carried out with a 29 to 30% hydrogen peroxide solution. The temperature in the reactor with catalyst located therein, the reaction mixture is passed through is to keep to about 5O ⁰ C. The volume velocity

speed of the oxidized products when passing through the catalyst is chosen to be 4 hours. The temperature in the reactor, in which one nachoxydiert the ozonolysis is maintained at about 80 ⁰ C, and the Durchleitvolumgeschwindigkeit of the reaction mixture is selected to be 0.5 Sf 'as the catalyst in the oxidation reactor is used the Sulfonsäureaustauscher K'J-2-8.

The thermal decomposition of oxidized ozonolysis is preferably carried out between 100 and 110 ⁰ C.

The advantages of the method according to the invention include:

By selectively reacting the ozone with the double bond and then using selective reagent, d. H. Hydrogen peroxide, no homologues of the dicarboxylic acids are formed, their removal from the end product presents great difficulties. Therefore, the end product does not need any special ones Cleaning testicles.

The use of a solid acid analyzer that it allows to work at high volume speeds (2 to 4 hours) and practically unlimited Has a lifespan and can be easily regenerated with hydrochloric acid

The iron ions entering the reaction mixture from the apparatus, the peroxide-like ozonolysis products can decompose, are exchanged for hydrogen ions by the synthetic resin ion exchanger and have no influence on the manufacturing process.

example 1

16.2 g (0.1 mol) of cyclododecatriene is dissolved in 64.8 g of 99.6% acetic acid and passes through the resulting solution at 20 ⁰ C ozonized air (2 wt .-% ozone) therethrough. During ozonolysis, 4.8 g of acetic acid are entrained in the air stream.

To the resulting in the ozonolysis 48.6 g ozonolysis product (quantitative conversion) in 42.0 g of acetic acid solution are added 38.0 g of 30% aqueous hydrogen peroxide solution, and the resulting mixture is stirred at 30 ⁰ C at a rate of 2St- by a conducted with the ka'ionenaustauscherharz KU-2-8-filled reactor leads to a second reactor, the mixture with the Volumgeschwindigkeit of 0.3 St ^{"Figure 1,} wherein the post oxidation of Ozonolyseprocdkts at 5O ⁰ C without catalyst is effected

The oxidized products coming from the second reactor are then subjected to thermal decomposition at 110 ^° C. for 2 hours. The aforementioned treatment gives succinic acid, which is isolated from the decomposition products in the following manner.

It drives the main fraction from (97%) of the acetic acid together with water at 40 ⁰ C and 13 Pa 332.2. The remaining acetic acid component is driven off at the same pressure and the same temperature as an azeotropic mixture after the addition of n-heptane (the n-heptane / acetic acid ratio is 6: 1).

When the azeotrope has been driven off, the succinic acid crystals remove traces of solvent 70 ° C dried for 2 hours.

35.2 g of succleic acid are obtained, which is 99.5% of theory or 217% by weight based on the reacted Cyclododecatriene

The succinic acid obtained in this way has the following characteristics:

Melting point

Acid number

Base material content according to information

the chromatographic analysis

185 to 185.5 ⁰ C 949 mg KOK / g

993%.

Example 2

16.2 g (0.1 mol) of cyclododecatriene are dissolved in 64.8 g 99.6% acetic acid and passes through the resulting solution at 25 ° C ozonated air (2 wt .-% ozone content) through. During ozonolysis, 4.8 g of acetic acid are entrained in the air stream.

To the resulting in the ozonolysis 48.6 g ozonolysis product in 42.2 g acetic acid solution 38.0 f 30% aqueous hydrogen peroxide solution are added, and the device obtained is FSCH at 50 ⁰ C with

fed at a rate of 4 ¹ St through the cation exchange resin with the KU-2-8-filled reactor

Then, to the second reactor daa mixture mi "the Volumgeschwindigkeit of 0.5 St ^-1 to where the post oxidation of the ozonolysis product at 8O ⁰ C without catalyst The further treatment of the reaction mixture is carried out as described in Example I.

35.0 g of succinic acid are obtained, which is 99.4% of the

jo theory or 217 wt .-%, based on the converted Cyclododecatriene, is The succinic acid produced in this way has the following characteristics:

Melting point 185 to 185.5 ° C

Acid number 949mgKOH / g ^j 'basic material content according to information

of the chromatographic analysis 99.9%.

jo example 3

For the oxidation of the products of cyclododecatriene ozonolysis among those described in Example 1 Conditions take 57.0 g of 20% aqueous

+ -, hydrogen peroxide solution. After the oxidation is conducted of the ozonolysis at 50 ⁰ C in the presence of Sulfonsäureaustauscherharzes Dowex 50 in the first reactor in which the reaction mixture at a rate of 4 St ', performed

μι, the post-oxidation of the ozonolysis products is carried out at 80 ° C. in the second reactor, into which the said mixture is passed at a rate of 0.05 St- ¹ . The oxidized products are further subjected to thermal decomposition at 90 ^° C. for 4 hours.

The succinic acid is isolated and purified under the conditions described in Example 1
This gives 34.8 g of succinic acid, which is 98.3%

M> of theory or 214% by weight, based on the converted cyclododecatriene, amounts to.

Characteristics of the end product:

Melting point

Acid number

Base material content according to information

the chromatographic analysis

185 to 185.5 ° C 949 mgKOH / g

Example 4

16.2 g of cyclododecatriene (0.1 mol) are dissolved in 56.8 g of 99.5% propionic acid. Through the resulting mixture is passed (5 wt .-% ozone) at 25 ⁰ C ozonated oxygen. 52.8 g (quantitative conversion) of the product of cyclododecatriene ozonolysis are formed in 32.6 g of propionic acid solution. 2.0 g of propionic acid are entrained in the stream of oxygen.

The further treatment of ozonolysis production (oxidation, post-oxidation and thermal decomposition) takes place as in example I.

The isolation of the acid thus formed from the decomposition products, which is a solution of succinic acid in aqueous propionic acid, is performed in the following manner: The major proportion of propionic acid (96%) together with water is driven off at 50 ⁹ C and 6666.1 Pa. The remaining propionic acid is driven off at the same pressure and the same temperature as an azeotropic mixture after the addition of ethylbenzene (the ethylbenzene-propionic acid ratio is 6: 1). After Azeotropabtrieb succinic acid crystals of Äthylbenzolspuren at 80 ⁰ C for 3 hours to be dried.

As a result, 34.6 g of succinic acid are obtained, what 97.6% of theory or 1212% by weight, based on the converted cyclododecatriene. amounts to.

Characteristics of the find product:

Melting point 185 to 186'C

Acid number «47 mg KOH / g base material content according to information

of the chromatographic analysis 99.6%.

Example 5

10.8 g (0.1 mol) of cyclooctadiene are dissolved in 52.0 g of glacial acetic acid and let through the resulting solution at 30.degree the ozonizers'; Air (1.5% ozone content).

There are 32.4 g (quantitative conversion) of the product of cydooctadiene ozonolysis in 36.0 g Acetic acid formed. 4.0 g of acetic acid are entrained by a stream of air.

The ozonolysis products are then treated with

25.0 g of 30% strength aqueous hydrogen peroxide solution. The mixture obtained is at 30 ° C with a Speed of 2 hours through the filled with the sulphonic acid exchange resin Amberlite 1 R 120 Passed through the reactor.

The further treatment of the reaction mixture is the same as that described in Example 1. You get

23.1 g of succinic acid, which is 99.0% of theory or 214 % By weight, based on the converted cyclooctadiene

Characteristics of the end product:

Melting point 186 to 186.5 C ^G

Acid number 948 mg KOH / g base material content according to information

of the chromatographic analysis 99.4%.

Example! 6th

11.0 g (0.1 mol) of cyclooctene are dissolved in 52.0 g of 99.6% strength acetic acid. Through the resulting solution is passed (2.5% ozone) at 25 ⁼ C ozonized air.

This gives 21.4 g (quantitative conversion) of the product of cyclooctene ozonolysis in 42.0 g of acetic acid solution. 4.0 g of acetic acid are entrained in the air stream.

12.4 g of 30% strength aqueous hydrogen peroxide solution are added to this solution.

The further treatment of the reaction mixture is the same as that described in Example 1.

The result obtained is 17.0 g of suberic acid, which is 97.7% of theory or 160% by weight, based on the converted cyclooctene. amounts to.

Characteristics of the product received:

Melting point 140 to 141 ° C

Acid number 645 mg KOH / g

Base material content according to information

ULI LI I I

Example 7

16.6 g ('.) ,! Mol) of cyclododecene is dissolved in 66.4 g of 99.6% acetic acid. Ozonized air (3% by weight ozone content) is passed through the solution obtained at 2 (TC). 27.2 g (quantitative conversion) of the product of cyclododecene ozonolysis in 54.4 g of acetic acid are formed. 6.0 g of acetic acid 12.7 g of 30% strength hydrogen peroxide solution are added to the product solution of the cyclododecene ozonolysis, after which the reaction mixture obtained is passed through the reactor filled with the cation exchange resin KU-2-8 at a rate of 2 hours ^: at a Reactor temperature of 30 ^c C conducts.

The mixture is then fed into the second reactor at a volume rate of OJ St ^: in which the post-oxidation of the ozonolysis products is carried out at 50 ° C. and without a catalyst. The mixture is then passed into a heat exchanger operated at 100 ° C. in which the oxidized products of the ozonolysis cyclododecane be decomposed during 3 hours, after cooling the solution to 20 ° C, the precipitated crystals of the 1,10-decane-dicarboxylic acid is filtered off, acetic acid traces with water cleaned: and dried at 80 ^c C for 3 hours.

The result is 22.8 g of 1.10-decanedicarboxylic acid. which is 99.1% of theory or 137% by weight, based on the converted cyclododecene.

Characteristics of the end product:

Melting point 128 ⁰ C

Acid number 486 mg KOH / g base material content according to information from

chromatographic analysis 993%.

Example 8

16.6 g (0.1 mol) of cyclododecene are dissolved in 66.4 g of 99.5% propionic acid. Through the resulting solution ozonized air is introduced at 40 ⁰ C (3 wt .-% ozone).

There are 28.6 g (quantitative conversion) of the product of cyclododecene ozonolysis in 54.6 g Propionic acid solution formed 5.0 g of propionic acid are entrained by the air stream.

The further treatment of the ozonolysis products is carried out under the conditions of Example 7.

The result is 22.3 g of 1,10-decanedicarboxylic acid, which is 98.0% of theory or 134% by weight, based on the converted cyclododecene is.

Characteristics of the end product:

Melting point 127.6 ° C

Acid number 487 mg KOH / g base material content according to information from

chromalographic analysis 99.9%.

Example 9

The amount of cyclododecene, the conditions for its ozonolysis and for the further treatment of Products correspond to those described in Example 7, with the exception that the oxidation of the ozonolysis products is carried out with 20.0 g of 20% strength aqueous hydrogen peroxide solution.

The result is 22.5 g of 1,10-decanedicarboxylic acid, which is 98.4% of theory or 134.5%, based on the converted cyclododecene.

Characteristics of the end product:

Melting point 128.2 ° C

Acid number 486 mg KOH / g

Basic material content according to the
chromatographic analysis

Example 10

98.9%.

The amount of cyclododecene, the conditions for its ozonolysis and for the further treatment of products correspond to those described in Example 7, with the exception that the products of cyclododecene ozonolysis are passed through a column filled with a solid acid catalyst Dowex 50 at a rate of 4 hours - 'passes at 6O ⁰ C and then supplies at a rate of 0.5 St ¹ to the second reactor, wherein the post oxidation of the ozonolysis products at 80 ° C and without a catalyst is carried.

The result is 22.2 g of 1,10-decanedicarboxylic acid, which is 97.5% of theory or 133.1% by weight, based on the converted cyclododecene.

Characteristics of the end product:

Mp 128.6 ⁰ C.

Acid number 488 mg KOH / g base material content according to information from

chromatographic analysis 98.0%.

Claims (1)

Claim: A method for preparing aliphatic dicarboxylic acids by ozonolysis of cycloolefins in the lower monocarboxylic acids, oxidation of the ozonolysis products by aqueous H ₂ OrLoSmIg between 30 and 60 ⁰ C, followed by thermal decomposition of the oxidized products between 90 and 110 ⁰ C, characterized in that the oxidation of the ozonolysis with the aqueous H ₂ OrLoSWIg in the presence of an acidic cation exchange resin as a catalyst