DE1194404B - Process for the preparation of perfluorocarbon sulfonamido compounds - Google Patents

Description

Process for the preparation of perfluorocarbon sulfonamido compounds A process for the preparation of perfluorocarbon sulfonamido compounds has been found found, which is characterized in that 1 mol of a compound of the formula Rf SOaN R1 Rs (I) where Rf is a perfluoroaliphatic radical of the formula CnFan or a perfiuorcycloaliphatic radical of the formula CnF2n + 1, in which n is a number is greater than 3, in particular 6 to 12, R1 is hydrogen or an alkyl radical at most 4 carbon atoms and R2 is hydrogen or an oxyalkyl radical with 2 to 4 carbon atoms means with at least 1 mole of divinyl sulfone in the presence of one reacts strongly basic catalyst in a manner known per se.

The reaction can be carried out with or without an inert organic solvent be made. It takes place at temperatures above 500 C, in particular at 80 up to 140 "C.

Preferably when reacting the reaction components in the absence an inert organic solvent, an excess of divinyl sulfone is used, to the addition of 2 molecules of the compound of formula I to a divinyl sulfone molecule to avoid. The excess of the divinyl sulfone used can then the implementation by suitable measures, such as recrystallization or distillation in vacuo, removed and used for further reactions.

Strongly basic, tertiary, aliphatic and / or heterocyclic amines, especially triethylamine or pyridine, as well as inorganic ones Bssen or their strongly basic salts can be used. Are particularly suitable Triethylamine or aqueous, about 500% solutions of sodium hydroxide or potassium hydroxide. The amount of the catalyst is preferably less than 5 percent by weight based to the compound of formula 1, in particular 0.5 to 20 / ,.

All solvents can be used as inert organic solvents Consider a sufficient dissolving power in the temperature range of the reaction for the compounds of formula 1 have.

Preferably, lower aliphatic ketones, such as acetone or methyl ethyl ketone, or aromatic hydrocarbons such as benzene, toluene or xylene are used.

When using a low-boiling solvent or a highly volatile one Catalyst, such as acetone or trimethylamine, it can be advantageous to start the reaction to increase the reaction rate at temperatures above the boiling point of Solvent in a suitable pressure vessel.

Aromatic, Higher boiling hydrocarbons have been shown to be possible from the resulting Reaction mixture to the compounds according to the invention by simple cooling isolate.

Because of their solubility in water, they can also be used in the reaction Catalysts can be easily removed. When using low-boiling Solvents such as acetone or methyl ethyl ketone, it can be advantageous after When the reaction has ended, the catalyst using a suitable strong inorganic To neutralize acid, add the solvent in vacuo at low temperature remove and, if necessary, the salt of the catalyst used by digestion remove with water.

Examples of suitable compounds of formula 1 are: N-methyl-perfluorobutane-sulfonamide, Perfluorooctane sulfonamide, N-ethyl-perfluorooctane-sulfonamide, N-ethyl-N-oxyethyl-perfluorooctane-sulfonamide and perfluorocyclohexane sulfonamide.

The production of these compounds takes place in a known manner, not here claimed manner by reacting the corresponding perfluoroalkyl or.

Perfiuorcycloalkylsulfonylhalogenide with ammonia or the corresponding primary amines or secondary alkyloxyalkylamines.

The compounds obtained according to the invention can be purified by purification be converted into crystallized form; for many technical purposes is one however, such cleaning is not necessary, since the implementation is very easy and extensive done quantitatively.

The process products serve as additives for paints and can for this z. B. with alkyd resins containing free hydroxyl groups are implemented.

It is already known to use vinyl ethers of N-hydroxyalkyl derivatives of To produce perfluoroalkylsulfonamides. Compared to these vinyl ethers, they have Vinylsulfone derivatives prepared according to the invention have a significantly higher reactivity the vinyl group. In particular, the vinyl sulfone derivatives store in contrast to the known vinyl ethers easily compounds with reactive hydrogen, in particular those compounds whose reactive hydrogen is bonded to a heteroatom, at.

Example 1 40 g of N-ethyl-N-hydroxyethyl-perfluorooctanesullonic acid amide and 11.8 g of divinyl sulfone are dissolved in 100 ml of acetone and 2 ml of 50 percent by weight NaOH added. The reaction mixture is heated to 100 for 3 hours in a stirred autoclave heated to 110 ° C.

After cooling, the solution is filtered and the solvent is in the filtrate removed in vacuo. The excess divinyl sulfone contained in the residue is distilled off in vacuo. The raw product is a yellowish, waxy mass. the Substance can be recrystallized from glacial acetic acid and then has a melting point of 68 to 70 ° C. Theoretically, the compound C8F1 7SO2N (C2H5) C2H4OC2H4SO2CH = CH2 contains 27.73 0 / C, 2.31% H and 9.270 / 0 S; found were 27.45% C, 2.36% H and 9,300 / 0 p.

Example 2 25.0 g perfluorooctanesulfonic acid amide and 5.9 g divinyl sulfone are dissolved in 100 ml of xylene and after adding 1 g of a 50 weight percent NaOH refluxed for 3 hours. After cooling, the solvent is filtered off and the residue is washed with water to remove the sodium hydroxide solution, whereby one after drying, a yield of about 95 ° / 0 0 / <> of crude product is obtained. After recrystallization from glacial acetic acid, the substance has a melting point of 202 to 205 "C. The formula C9F17SO2NHC2H4SO2CH = CH2 contains 23.50% C, 1.20% H and 10.50% S; found 23.31 to C, 1.111 <> H and 10.20% 5.

Example 3 If, in the same way as stated in Example 2, 0.05 mol of N-ethyl-perfluorobutanesulfonic acid amide with 0.05 mol of divinyl sulfone, so one receives the N-vinylsulfonäthyl-N-ethyl-perfluorobutanesulfonic acid amide with about 96% yield.

Example 4 26.4 g of N-ethyl perfluorooctanesulfonic acid amide are added to 100 ml of methyl ethyl ketone and 5.9 g of divinyl sulfone dissolved, 1 ml of 50 weight percent NaOH added and im Stirring autoclave heated to 100 to 110 ° C for 3 hours. After cooling, the solvent becomes separated from the precipitated reaction product by filtration and the filter residue washed with a little methyl ethyl ketone. The raw yield of the corresponding Vinylsulfonäthylderivat is 30 g, which corresponds to 93010 of theory. The substance leaves Purify yourself further by recrystallizing from toluene.

Example 5 38 g of N-ethyl-N-oxyethyl-perfluorooctanesulfonamide, 10 g Divinyl sulfone and 1 g of triethylamine are mixed with 100 g of toluene and placed in a stirred autoclave Heated to 100 ° C for 4 hours. After cooling to room temperature, the solvent will be and the catalyst is distilled off in vacuo at water bath temperature and the oily-waxy one The residue is dried over silica gel in vacuo, with crystallization occurring.

The crude yield is 96%. The product can be made according to the example 1 recrystallize.

Example 6 41.1 g of 4-trifluoromethyl decafluorocyclohexanesulfonic acid amide (= 0.1 mol) are mixed with 11.8 divinyl sulfone (= 0.1 mol) and 1 g of pyridine in 100 ml Dissolved acetone and heated to 100 to 1200C in a stirred autoclave for 4 hours. To At the end of the reaction, acetone and pyridine are distilled off, the vinyl sulfone derivative remains as a brown waxy mass. The product can be recrystallized can be purified from toluene.

Comparative experiments An alkyd resin was produced according to the specification in Ullmann's Encyclopedia of Industrial Chemistry, 3rd Edition, Vol. 14, p. 103, example 3: 423 g of linseed oil and 274 g of glycerine were transesterified at 250 to 2600 C and then reacted further with 560 g of phthalic anhydride and 50 g of xylene, first at 200.degree and finally at 160 to 180 ° C.

Of this A. 1 part by weight in 3 parts by weight of methyl ethyl ketone dissolved (= solution A), B. 1 part by weight and 0.1 part by weight of the reaction product from Perfluorooctansulfonsäureamid and divinyl sulfone in 3 parts of methyl ethyl ketone solved (= solution B).

Aluminum sheets and both sheets were coated with both solutions Dried 1½ hours at 160 ° C. B had a better surface hardness in Scratching as well as better oil repellency can be noticed.

To measure the latter, a drop of paraffin oil DAB 6 (approx 0.1 cm3) and measured the contact angle from this. This amounted to the sheet treated with solution A 15 ° and the sheet treated with solution B 90 °. Even after standing for a long time, the values did not change.

In addition, the oil drop at B was much easier to use using filter paper be sucked off than with A.

Claims (3)

Claims: 1. Process for the production of perfluorocarbon sulfonamido compounds, d a d u r c h e denotes that one mol of a compound of the formula R'SO2NR1R2 wherein Rf is a perfluoroaliphatic radical of the formula CnF2n + 1 or a perfiuorcycloaliphatic Remainder of the formula CnF2n-1, in which n is an integer greater than 3, in particular 6 to 12 is R, hydrogen or an alkyl radical with at most 4 carbon atoms and R2 is hydrogen or an oxyalkyl radical with 2 to 4 carbon atoms means with at least 1 mole of divinyl sulfone in the presence of a strongly basic one Reacts catalyst in a known manner. 2. The method according to claim 1, characterized in that the implementation is carried out in an inert organic solvent. 3. The method according to claims 1 and 2, characterized in that that the reaction takes place at temperatures above 50 "C, preferably at 80 to 140" C, is made. Publications considered: Ho u b e n - W e y 1, »Methods derorganic chemistry, IX, (1955), p. 247.