Method for preparing perfluorocyclohexene 1-carboxylic acid fluoroanhydride or perfluorocyclohexane carboxylic acid fluoroanhydride

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for synthesis of perfluorocyclohexene 1-carboxylic acid fluoroanhydride or perfluorocyclohexane carboxylic acid fluoroanhydride. Method involves decarbonylation of perfluorohexane dicarboxylic acid 1,2-difluoroanhydride at temperature 150-450°C in the presence of catalyst, namely, aluminum trifluoride applied on aluminum oxide, or activated carbon promoted with potassium fluoride wherein the content of metal fluorides in catalyst is 10-40 weight% to form perfluorocyclohexene 1-carboxylic acid fluoroanhydride that is isolated as the end product, or subjected to further fluorination with gaseous fluorine in inert solvent medium at temperature from -20°C to 50°C and isolation of perfluorocyclohexane carboxylic acid fluoroanhydride by rectification.

EFFECT: improved method of synthesis.

2 cl, 8 ex

 

The invention relates to organofluorine chemistry, in particular to a method of producing foramerican perftorirovannogo and perftorirovannogo acids used for the synthesis of monomers, surfactants and heat-resistant polymers with water - and oil-repellent properties.

A known method of producing foramerica perftorirovannogo acid (FA PFZGC) direct fluorination of benzoyl chloride with gaseous fluorine diluted with an inert gas at cryogenic temperatures (minus 78° (C) /US 4400532, 23.08.83/.

A known method for simultaneous obtaining of foramerican perftorirovannogo and perftorirovannogo acids, which consists in the fluoridation of pentafluorobenzaldehyde the cobalt TRIFLUORIDE at 135° /J. Fluor. Chem., 1984, v.25, No. 2, R/.

The main disadvantage of the above methods is the low yield of the target product, which does not exceed 20%.

The most common method of obtaining foramerica perftorirovannogo acid is an electrochemical fluorination (ECF) of aromatic acids and their derivatives in the environment of anhydrous hydrogen fluoride.

Known electrochemical synthesis of foramerica perftorirovannogo acid from benzoyl chloride /US 3683036, 8.08.72/. Product ECF contains 47% FA PFCG IS TO, 21% of foramerican 2 - and 3-performancecheckinterval acid, 20% non-inert compounds, such as pervertibles and other, 12% unidentified foramerican.

Known electrochemical synthesis of foramerica perftorirovannogo acid from dehalogenation and dimethyl esters of phthalic acid /US 3028321, 30.04.62; Fluorine-containing compounds. Directory, Cherkassy, 1985/. This, along with the desired product is formed 20-40% byproduct of diferenciada perftorirovannogo acid that does not have sales areas.

Method of electrochemical fluorination based on the use of cheap hydrocarbons and allows you to get the F PFZGC with the release of 30-50%, but the selectivity of the ECF process is not sufficiently high due to the formation of a wide range of products, some of which finds further application.

The objective of the invention is to develop a method of producing foramerican perftorirovannogo and perftorirovannogo acids with high yield of by-product ECF derivatives of phthalic acid.

This object is achieved by decarbonylation of diferenciada perftorirovannogo acid in the presence of a catalyst at a temperature inlet 150 up to 450°education foramerica perverts celexaincrease acid, which is marked as the target product or subjected to fluorination with gaseous fluorine in an inert solvent at a temperature from minus 20 to 50°obtaining FA PFZGC.

In the study of reaction decarbonylation of diferenciada perftorirovannogo acid was found that in certain conditions it proceeds according to the following scheme:

i.e. carbonyliron subjected to one foramerica group, which leads to the formation of foramerica pervertibles-1-carboxylic acid (FA PFCG-1-QC).

As a result of further fluorination of foramerica perftorirovannogo acid is joining fluorine double bond with the formation of foramerica perftorirovannogo acid

The process of carbonyliron carried out in continuous mode in a tubular reactor filled with a catalyst (the fill factor of the reactor is 0.8). The reactor is equipped with electric heating, pipes for supplying a source of reagent and reaction products.

The raw material for the synthesis is deferredread perftorirovannogo acid, ECF received dimethylphthalate in the medium of anhydrous hydrogen fluoride, which is a mixture of isomers, with the present mainly of 1,2-diferenciada perftorirovannogo acid (1,2-DFA PTZGGK).

For synthesis can be used as pure deferredread perftorirovannogo acid and its mixture with other inert organofluorine compounds - the ultimate foramerican and fluorocarbons, which are by-products of ECF. The content of 1,2-DFA PTZGGK in the mixture is typically 50-60%.

Carbonyliron carried out at atmospheric pressure in a stream of inert gas and the temperature range inlet 150 up to 450°C. At lower temperatures significantly reduced the conversion of the original diferenciada perftorirovannogo acid, and by raising the reaction temperature above 450°decreases the yield of the target product foramerica pervertibles-1-carboxylic acid due to the formation of side connections.

As the catalyst used aluminum TRIFLUORIDE, deposited on alumina, or activated carbon promoted with potassium fluoride.

The amount of metal fluoride in the catalyst ranges from 10 to 40 wt.%. Within this interval, the change in the concentration of fluoride does not affect the yield of the target product. The decrease in concentrations of less than 10 wt.% leads to reduction of yield. An increase of more than 40 wt.% not significantly affect the process. When studying the reaction of catalytic decarbonylation it was found that the catalyst KF/St. about lady much higher activity compared to AlF 3/Al2O3.

The resulting product carbonyliron (raw) contains up to 55% of foramerica pervertibles-1-carboxylic acid, which is isolated in the form of the desired product by distillation and identified by IR and NMR19F-spectroscopy.

Output F PFCG-1-QC is over 90%.

Further fluorination subject as pure floramite pervertibles-1-carboxylic acid, and obtained from the stage of raw decarbonylation.

For fluorination using elemental fluorine or fluorine diluted with an inert gas such as nitrogen. In this case, the fluorinating mixture can contain up to 70% of the inert diluent.

The process is carried out in a flow reactor equipped with a siphon to feed fluorinating mixture, thermocouple and the outlet pipe.

For a more complete reaction of the fluorine served from 1.2 to 3.0-fold excess of the stoichiometric required. Submission of fluorine in more inappropriate as it does not lead to further increase in the yield of the target product.

The reaction is carried out at normal or excess pressure of 0.7 kgf/cm2in the temperature range from minus 20 to 50°With, mainly at room temperature. Further decrease of the temperature of the process leads to high energy consumption, and at temperatures above 50°C is the DNA of the target product at the expense of the growth of its partial pressure.

The process of fluorination is carried out in an inert solvent, which take from one to three volumes to the original mixture. As the inert solvent use by-products of the ECF dimethylphthalate.

Floramite perftorirovannogo acid is recovered from the reaction mixture by distillation and analyzed by GLC. The yield of the target product is above 90% based on loaded FA PFCG-1-CC and up to 80% based on the original deferredread perftorirovannogo acid. Gas stavki containing unreacted source reagents, sent for chemical lime absorber.

Thus, the developed method allows you to dispose of waste electrochemical fluorination derivatives of phthalic acid in useful industrial products, thereby expanding the raw material base for receiving foramerican perftorirovannogo and perftorirovannogo acids, as well as the opportunity cheap and technologically simply get these products with high yields.

The following examples illustrate the invention but do not restrict it.

Example 1. Synthesis of foramerica pervertibles-1-carboxylic acid. In a tubular reactor made of stainless steel with a capacity of 0.3 is m 3download 0,25 DM3catalyst comprising an activated carbon promoted with potassium fluoride in the amount of 35 wt.%. The catalyst was calcined in a stream of nitrogen at 350-400°C for 10 hours. The temperature was then raised to 450°miss nitrogen at a speed of 1.0 DM3per hour and dosed 181 g of a mixture of by-products ECF of dimethylphthalate containing 48 wt.% 1,2-DFA PTZGGK with a speed of 128 g/hour.

Coming out of the reactor, the gas mixture is passed through the condenser, water cooled and condenses in the receiver. Received to 118.0 g of condensate containing 55,1 wt.% foramerica pervertibles-1-carboxylic acid. After rectification of raw receive 65 g FA PFCG-1-QC, BP. 95-96°C, d420=1,62 g/cm3. The output of 91.7%.

Examples (2-4) is carried out under conditions analogous to example 1

Example 2. Charged to the reactor activated carbon promoted with potassium fluoride in an amount of 10 wt.%, and miss at 50 g/h 175 g of a mixture of by-products ECF of dimethylphthalate containing 48 wt.% 1,2-DFA PTZGGK. The temperature of the reaction support 250°C. After condensation receive 124,0 g raw, which rectificatum and release of 63.6 g F PFCG-1-QC. The output is of 92.9%.

Example 3. Charged to the reactor activated carbon promoted with potassium fluoride in the amount of 40 wt.%, and crossing the t with a speed of 42.8 g/h 342,0 g of a mixture of by-products ECF of dimethylphthalate, containing 48 wt.% 1,2-DFA PTZGGK. The temperature of the reaction support 350°C. After condensation receive 224,0 g raw, which rectificatum and release of 123.2 g F PFCG-1-QC. The output is 92,3%.

Example 4. Charged to the reactor aluminum TRIFLUORIDE deposited on the aluminum oxide in the amount of 25 wt.%, and miss with the speed of 9.4 g/h 50 g of a mixture of by-products ECF of dimethylphthalate containing 48 wt.% 1,2-DFA PTZGGK. The temperature of the reaction support 150°C. After condensation receive of 39.2 g of raw sugar, which rectificatum and allocate 12.5 g F PFCG-1-QC. The output is 54.8%.

Example 5. Synthesis of foramerica perftorirovannogo acid

In the reactor of stainless steel with a capacity of 500 ml load 65 g foramerica pervertibles-1-carboxylic acid, obtained in example 1, and 65 g of inert perfluorocarbon - products ECF of dimethylphthalate. Then the temperature is reduced to 5°and through the siphon serves 6,2 liters of fluorine gas in a mixture with nitrogen at a ratio of 1:1 within 30 minutes the pressure in the reactor support of 0.5 kgf/cm2.

From the resulting reaction mixture by distillation allocate to 68.4 g foramerica perftorirovannogo acid, BP. 78°C. the Yield of the target product is 93.1%of.

Example 6. Synthesis of foramerica perftorirovannogo acid.

Is an is logical to example 5. Charged to the reactor 120 g foramerica pervertibles-1-carboxylic acid, 200 g of by-products ECF of dimethylphthalate and serves to 13.9 liters of fluorine gas in a mixture with nitrogen at a ratio of 1:0.5 V for 1 hour. The pressure in the reactor support 0.1 kgf/cm2temperature 50°C.

From the resulting reaction mixture by distillation allocate 128,2 g foramerica perftorirovannogo acid, BP. 78°C. the Yield of the target product is 94,5%.

Example 7. Synthesis of foramerica perftorirovannogo acid

In the reactor described in example 1 load of 0.25 DM3catalyst comprising an aluminum TRIFLUORIDE deposited on the aluminum oxide in the amount of 15 wt.%. The catalyst was calcined in a stream of nitrogen at 350-400°C for 10 hours. Then at a temperature of 400°miss nitrogen at a speed of 1.0 DM3per hour and dosed with a speed of 10.5 g/hour of 42.0 g of a mixture of by-products ECF of dimethylphthalate containing 56 wt.% 1,2-DFA PTZGGK.

Coming out of the reactor, the gas mixture is passed through the condenser and condense in the receiver, where the raw number 29,0 g fed into the reactor described in example 2. There is load of 70 g of by-products ECF of dimethylphthalate and within 5 min through a siphon serves 1.2 l of fluorine gas. The temperature in the reactor support 24°C, a pressure of 0.65 cgsm 2. The resulting reaction mixture rectificatum and release 11.2 g of foramerica perftorirovannogo acid. The yield of the target product is 51.8%.

Example 8. Synthesis of foramerica perftorirovannogo acid.

In the reactor described in example 1 load of 0.25 DM3catalyst comprising an activated carbon promoted with potassium fluoride in an amount of 20 wt.% The catalyst was calcined in a stream of nitrogen at 350-400°C for 10 hours. Then at a temperature of 300°miss nitrogen at a speed of 1.0 DM3per hour and dosed 181,0 g of a mixture of by-products ECF of dimethylphthalate containing 48% 1,2-DFA PTZGGK speed 94,7 g/hour.

Coming out of the reactor, the gas mixture is passed through the condenser and condense in the receiver, where the raw number to 118.0 g fed into the reactor described in example 2. There also loads of 336 g of by-products ECF of dimethylphthalate and within 40 min through a siphon serves 10 liters of fluorine gas in a mixture with nitrogen. The temperature in the reactor support minus 10°C. the resulting reaction mixture rectificatum and release of 68.3 g of foramerica perftorirovannogo acid. The yield of the target product was 85.1%.

1. The method of producing foramerica pervertibles-1-carboxylic acid or foramerica perftorirovannogo KIS is the notes, including carbonyliron 1,2-diferenciada perftorirovannogo acid at a temperature inlet 150 up to 450°in the presence of a catalyst, such as aluminum TRIFLUORIDE, deposited on alumina, or activated carbon promoted with potassium fluoride, and the fluoride content of metals in the catalyst is from 10 to 40 wt.%, with the formation of foramerica pervertibles-1-carboxylic acid, which is isolated in the form of the target product or subjected to further fluorination with gaseous fluorine in an inert solvent at a temperature from minus 20 to 50°emitting foramerica perftorirovannogo acid by distillation.

2. The method according to claim 1, characterized in that as the inert solvent used, by-products of the electrochemical fluorination of dimethylphthalate.



 

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(1)

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3 cl, 2 tbl, 14 ex

FIELD: chemistry.

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2 cl, 3 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for synthesis of perfluorocyclohexene 1-carboxylic acid fluoroanhydride or perfluorocyclohexane carboxylic acid fluoroanhydride. Method involves decarbonylation of perfluorohexane dicarboxylic acid 1,2-difluoroanhydride at temperature 150-450°C in the presence of catalyst, namely, aluminum trifluoride applied on aluminum oxide, or activated carbon promoted with potassium fluoride wherein the content of metal fluorides in catalyst is 10-40 weight% to form perfluorocyclohexene 1-carboxylic acid fluoroanhydride that is isolated as the end product, or subjected to further fluorination with gaseous fluorine in inert solvent medium at temperature from -20°C to 50°C and isolation of perfluorocyclohexane carboxylic acid fluoroanhydride by rectification.

EFFECT: improved method of synthesis.

2 cl, 8 ex

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