DE2303925C3 - 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 FR-PS 13 91338 is a method for Production of dicarboxylic acids by ozonolysis of the cyclododecene in the solution of lower monocarboxylic acids at 25 ° C with subsequent oxidation decomposition of the ozonolysis products in the oxygen or Air flow with gradually increasing temperature from 80 to 110 ° C is described. Because the thermal Oxidation decomposition of the ozonolysis products of the formula

OOH

C- (CH ₂ ) - 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 makes the process of producing the acid of required quality complicated. It is necessary to employ complicated and expensive purification methods. The yield of the end product in the known processes does not exceed 70% of theory

FR-PS 11 73 225 describes a process for the production of haloglutaric acids using H2SOa 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 H ₂ SO ₄ , NH _{3 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 preparation of polycarboxylic acids from substituted alkylcyclohexanes by oxidation of 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 are _{oxidized with an aqueous H 2} O ₂ -LoSUHg in the presence of a strong mineral acid

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 with an aqueous H ₂ O ₂ -LoSUHg in the presence of a strong one Mineral acid oxidized _{in CH 3} COOH at a pH of 2 or less

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

cyclic olefins with one or more double bonds to ozonides and in the hydrolysis of the same and oxidation with O ₂ or an O 2 -containing gas in the presence of catalysts (KMnO ₄ , Cr ₂ O ₃ , Co ₂ O ₃ ) organic liquids are used in which the starting olefin and the ozonolysis product are soluble, especially 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

/ (CHA

CH

n = 4 to 10

CH

in solvents, preferably in propionic acid with subsequent oxidative decomposition of the ozonization products. The oxidizing agent is O ₂

J5 used with a low ozone content

This reference is not relevant for the following reasons:

Monocarboxylic acids are proposed as solvents for ozonization, but in particular pro pionic 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 in the presence of O ₃ (it is also possible to use Oxidation initiation 5 catalysts and catalysts specified) takes place.

In US-PS 34 41 604 a process for the preparation of dicarboxylic acids by ozonolysis of Cycloolefins in the solution of monocarboxylic acids with subsequent oxidation of the ozonolysis products with air or O2 in the presence of 10 to 35 wt .-% H ₂ O described.

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 invalid for the following reasons relevant:

In the process according to the invention, on the other hand, the ozonolysis products with an aqueous H2O ₂ solution in the presence of acidic cation exchange resins as a catalyst, in particular of cation

ho exchangers, obtained by polymerizing styrene and divinylbenzene with ion exchange groups SO ₃ H (KU-2-8), oxidized and then thermally converted. This process of converting ozonolysis products leads to an increase in the

b5 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 ozonolysis between 20 and 40 ° C in lower monocarboxylic acids (e.g. 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. KU-2-8 or US ion exchange resin Amberlite 1 R 120 (see the book by N. T. Polianski "Katalis ionitamie, M, Chemie" pages 7,8,9,10,11,12

and 204, 206) is present, passed through the addition of hydrogen peroxide obtained after the reaction mixture between 30 and 60 ° C with a Volumgeschwindigkeit 2-4 St. ¹ The reaction mixture then enters the second reactor at a volume rate of 03 to 05 St- ', 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:

U CH ₃ COUH + H ₂ O ₂ <= ± CH ₃ CO ₃ H + H ₂ O O OOH O OH OOH OH OOH

! I I I! I I Il

2. CH ₃ CO ₃ H + C (CH ₂ J ₁₀ -CH »CH ₃ C-CO-CH- (CH ₂ ), o CH 'CH ₃ COOH + C (CH ₂ J ₁₀ CH

H OCOCH ₃ OCOCH ₃ O 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 In the second stage, the ozonolysis product is homogeneously oxidized with the peracetic acid in the absence of the acid catalyst.

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

This reaction is carried out in the absence of a catalyst at a temperature between 90 and RO ⁰ C for 2 to 4 hours and proceeds according to the following scheme:

HO OOH C (CH ₂ J ₁₀ -CH -

OCOCH ₃

OH O

Il

►C- (CH ₂ J ₁₀ -C + CH ₃ COOH O OH

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

The isolation of the dicarboxylic acids from the decomposition products that form a dicarboxylic acid solution in represent aqueous monocarboxylic acid, and their purification will depend 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 proportion of the acid mentioned (3 to 5%) is at the same residual pressure and the same temperature as an azeotropic mixture after the addition of a appropriate solvent (n-heptane when using acetic acid as the reaction medium or Ethylbenzene when using propionic acid) is driven off.

The monocarboxylic acid / solvent ratio is 1: 6.

After the azeotropic distillation has ended, traces of succinic acid and suberic acid crystals are dried between 70 and 80 ^° C. for 2 to 3 hours.

To obtain the 1,10-deca.ndicarboxylic acid from aqueous To isolate the monocarboxylic acid solution, a mixture coming from the oxidation reactor is passed through Products in a operated at 100 ° C, a heat exchanger, in which the oxidized products decompose the cycloolefin ozonolysis, then the solution is cooled to 15 to 2O ⁰ C., purified water, precipitated crystals of the 1,10-decanedicarboxylic of monocarboxylic traces of bonsic acid and dries 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

the degree of purity thus determined for 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

bo their relatively high cost and lower

Useful because solutions of ozonolysis products

the compounds mentioned are heavier in these acids are separable.

The oxidation of ozonolysis products is with 29-

b5 to 30% hydrogen peroxide solution to be carried out. 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 St ^-1 . The temperature in the reactor in which the ozonolysis products are post-oxidized is kept at around 80 ° C, and the flow rate of the reaction mixture is selected to be 0.5 St- '/ J the catalyst in the oxidation reactor is the sulfonic acid exchanger KU-2-8.

The thermal decomposition of oxidized Ozonolyssprodukte 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, are formed no homologs of the dicarboxylic acids, the removal of which from the end product presents great difficulties That is why the end product does not need any special cleaning methods.

The use of a solid acid catalyst 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 that enter the reaction mixture from the apparatus and that can decompose peroxide-like ozonolysis products are exchanged for hydrogen ions by the synthetic resin ion exchanger and have no effect on the production process Influence off.

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 container filled with the cation exchange resin KU-2-8 reactor leads then passed to a second reactor, the mixture with the Volumgeschwindigkeit of 03 to St ^1, wherein the post oxidation of the ozonolysis product at 5O ⁰ C without catalyst is effected

The oxidized products coming from the second reactor are then subjected to a thermal one Decomposition at 110 ° C for 2 hours. Through the Treatment called succinic acid is obtained, the isolation of which is based on the decomposition products is done in the following way.

The main part (97%) of the acetic acid is driven off together with water at 40 ° C. and 13,332.2 Pa. Of the remaining acetic acid is at the same pressure and the same temperature as an azeotropic mixture according to the Addition of n-heptane abgen JiI ^ n (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 succinic acid are obtained, which is 99.5% of the Theory or 217 wt .-% based on the converted cyclododecatriene is

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

Melting point 185 to 185.5 "C

Acid steel 949mgKOK / ₂ grand substance content according to information

of the chromatographic analysis 99.9%.

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 ozonized air (2 wt .-% ozone content). During ozonolysis, 4.8 g

Acetic acid entrained by the air stream.

There are 48.6 g of ozonolysis product in 42 g of acetic acid solution formed during ozonolysis 38.0 g of 30% strength aqueous hydrogen peroxide solution are added, and the mixture obtained is at 50 ° C with a speed of 4 hours through the reactor filled with the cation exchange resin KU-2-8 directed

Then one leads to the second reactor, the mixture with the volume rate of 0.5 St- '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. 1 35.0 g of succinic acid are obtained, which is 99.4% of the 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 base material content according to information

of the chromatographic analysis 99.9%.

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 ¹ St performed

Thus, taking the post oxidation of the ozonolysis products prior at 80 ⁰ C in the second reactor is fed into the said mixture at a rate of 0.05 St. ¹ The oxidized products undergo further thermal decomposition at 90 ^° C. during Subjected to 4 hours.

The isolation and purification of the succinic acid are carried out as described in Example 1 Conditions. This gives 34.8 g of succinic acid, which is 98.3% of theory or 214% by weight, based on the converted cyclododecatriene is

Characteristics of the end product: Melting point 185 to 185.5 ° C

Acid number 949 mg KOH / g base material content according to information

of the chromatographic analysis 99.9%.

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 ° / o ozone content) 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 the ozonolysis products (oxidation, post-oxidation and thermal decomposition) takes place as in example 1.

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 5O ⁰ 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, which is 97.6% of theory or 212% by weight, based on the converted cyclododecatriene is.

Characteristics of the end product:

Melting point 185 to 186 ° C

Acid number 947 mg KOH / g base material content according to information

of the chromatographic analysis 99.6%.

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

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

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

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

Characteristics of the product received:

Melting point 140-141 ° C

Acid number 645 mg KOH / g base material content according to information

of the chromatographic analysis 99.5%.

Example 5

10.8 g (0.1 mol) of cyclooctadiene was dissolved in 52.0 g glacial acetic acid and passes through the resulting solution at 30 ⁰ C, the ozonized air (1.5% ozone).

There are 32.4 g (quantitative conversion) of the product of cyclooctadiene 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 resulting mixture is passed at 30 ⁰ C at a rate of 2 St 'through the filled with the Sulfonsäureaustauscherharz Amberlite 1 R 120 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 ⁰ C

Acid number 948 mg KOH / g ^b0 base material content according to information

of the chromatographic analysis 99.4%.

Example 6

b5

11.0 g (0.1 mol) of cyclooctene are dissolved in 52.0 g 99.6% acetic acid. Air that has been ozonated at 25 ° C. (2.5% ozone content) is passed through the solution obtained.

Example 7

16.6 g (0.1 mol) of cyclododecene are dissolved in 66.4 g of 99.6% acetic acid. Air (3% by weight ozone content), ozonated at 20 ° C., is passed through the resulting solution. 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 is entrained in the air stream. 12.7 g of 30% strength hydrogen peroxide solution are added to the product solution from 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- ¹ at a reactor temperature of 30 ° C.

The mixture is further supplied with a Volumgeschwindigkeit of 03 St 'in the second reactor, in which the post oxidation of the ozonolysis is carried out at 50 ⁰ C and with no catalyst. Then passing the mixture in an operated at 100 ⁰ C heat exchanger in which the oxidized products of the ozonolysis cyclododecane be decomposed during 3 hours, after cooling the solution to 20 ⁰ C, the precipitated crystals of the 1,10-decanedicarboxylic filtered from traces of acetic acid-cleaned with water and dried at 8O ⁰ 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 is.

Characteristics of the end product:
Melting point

128 ° C

486 mg KOH / g

99.5%.

Base material content according to information from the chromatographic analysis

Example 8

16.6 g (0.1 mol) of cyclododecene are dissolved in 66.4 ^{% or} 99.5% propionic acid. By the obtained Lösunf 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 { Propionic acid solution formed 5.0 g of propionic acid who entrained by the air stream.

The further treatment of the ozonolysis product 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.

H)

Characteristics of the end product:

Melting point
Acid number

128.2 ⁰ C

486 mg KO H / g

Basic material content according to the
chromatographic analysis 98.9%.

Characteristics of the end product:

Mp 127.6 ⁰ C.

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

chromatographic 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

Example 10

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 through a column filled with a solid acid catalyst Dowex50 with a Speed of 4 hours at 60 ° C and then with at a rate of 0.5 hours' fed to the second reactor, in which the post-oxidation of the ozonolysis products takes place at 80 ° C and without a catalyst.

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:

Melting point 128.6 ° C

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

chromatographic analysis 98.0%.

Claims (1)

Claim: Process for the preparation of aliphatic dicarboxylic acids by ozonolysis of cycloolefins in lower Monocarboi acids, oxidation of the ozonolysis products by means of aqueous H ₂ OrLoSUHg between 30 and 60 ° C and subsequent thermal decomposition of the oxidized products between 90 and HO ⁰ C, characterized in that the oxidation of Ozonolysis products carried out with the aqueous H ₂ O ₂ -LoSUHg in the presence of an acidic cation exchange resin as a catalyst.