DE1948993A1 - Perfluorocarboxylic acid derivs - Google Patents

Abstract

Perfluorocarboxylic acid deriv. of formula:- where Rf is C3-C11 perfluoroalkyl; R1 is lower alkyl, -(CH2)2-NH2, or -CH(CH3)CH2-NH2; R2 and R4 are lower alkylene; R3 is H or a lower alkyl; R5 is -O-, -NH-, or -(NH2)- and z is 0 - 3. The compounds are used as oleophobic agents for textiles etc.

Description

Perfluorocarboxylic Acid Derivatives The invention relates to new perfluorocarboxylic acid hydrazides and the use of these new substances as oil repellants.

The compounds correspond to the general formula: in RF a perfluoroalkyl radical with 3 to 11, preferably 5 to 10 carbon atoms, R1 a hydrogen atom, a low molecular weight alkyl radical or a radical of the formula -CH2-CH2-NH2 or -C, H-CH2-NH2, 2 a CH3 low molecular weight alkylene radical, R3 is a hydrogen atom or a low molecular weight alkyl radical, R4 is a low molecular weight alkylene radical, R5 is the radical -O-, -NH- or -NH-NH- and z is zero or an integer from 1 to 3.

The radicals designated as low molecular weight are preferably such with up to 6 carbon atoms; Particular emphasis is given to alkyl radicals with 1 to 3 and alkylene radicals with 2 to 3 carbon atoms.

The perfluoroalkyl radical can, for example, be derived from perfluorocapric acid, perfluorocaproic acid or derive perfluorocaprylic acid. Due to the usual manufacturing process these acids often contain up to about 15% higher fluorinated carboxylic acids with up to 12 carbon atoms.

Because of their easy accessibility, compounds with RF = CF3- (CF2) 6-, R1 and R3: H and R5 = -NH-Individual representatives of the new compounds are, for example, the substances of the formulas: CF3- (CF2) 6-CO- NH-NH- (CH2) 2-NH-CO- (CF2) 6-CF3 CF3- (CF2) 6-CO-NH-NH- (CH2) 2-NH- (CH2) 2-NH-CO- (CF2) 6-CF3 CF3- (CF2) 10-CO-NH-NH (CH2) 2-NH-NH-CO- (CF2) 10-CF3 CF3- (CF2) 6-CO-NH-NH- (CH2) 2-NH- (CH2) 3-NH-CO- (CF2) 6-CF3 CF3- (CF2) 6-NH-NH- (CH2) 2-NH- (CH2) 2-NH- (CH2) 2-NH-NH-CO- (CF2) 6-CF3 The fabrics of the. general formula I are accessible in a manner known per se. For example, you can use a hydrazine of the general formula: in which R1, R2, R3, R4 and R5 and z have the aforementioned meaning, in the presence of an acid acceptor, for example an alkali metal hydroxide or preferably a tertiary amine, such as triethylamine or ethyldiisopropylamine, with a perfluorinated carboxylic acid halide RF-CO-Cl or better with a perfluorinated carboxylic acid ester RF-COOR ', where RF has the abovementioned meaning and R' denotes a low molecular weight alkyl radical, preferably OH - or 3 C2H5-, in a ratio of 1: 2.

The hydrazines of general formula II are known in the art, e.g. accessible from the corresponding alkylenimines and hydrazine.

The following way of working has proven itself: In an indifferent Solvents such as benzene, toluene, methylene chloride, chloroform, carbon tetrachloride or, preferably methanol or ethanol, a compound of the formula II is initially introduced and gives the perfluorocarboxylic acid ester at least twice as molar at room temperature Amount, based on the compound of the formula II, to it. The reaction mixture is stirred then another 4 to 5 hours at 40 to 50 ° C. and at least 10 hours at room temperature after. The resulting bisperfluoroacyl compound is isolated in the customary manner and dried.

The substances of the formula I fall as yellowish, crystalline substances or mostly in the form of yellow to brown pastes that are in organic solvents, such as acetone, methanol, ethanol and acetic acid, are soluble.

The substances according to the invention are very suitable as oil repellants For surfaces of all kinds. They are of particular importance for making them oil-repellent of fibers made from natural and man-made materials such as wool, silk Polyamide fibers, Polyester, polyolefin, cellulose ester fibers and in particular natural fibers and regenerated cellulose and their blends with synthetic fibers. The fabrics of the formula I can be in the form of their solutions in organic solvents or in Form aqueous dispersions of these solutions or of the substances themselves on the to be treated Surfaces are applied, The solutions applied to the surface or Dispersions are then made at ordinary or, preferably, elevated temperature dried. After the solutions or dispersions have dried, the surfaces are oleophobic. When treating textile goods, the finishing effects are special washable if the textiles impregnated with the substances of the formula I are used after drying heated for a few minutes at 800 to 1500C.

The effects are mainly due to cellulose containing or derived from it existing material very pronounced and achieve with an application of approx 0.8% of the substance according to the invention, based on the dry textile material, already the optimum.

The resistance of the equipment, especially against the effects of water and against washing, can be vastly improved if one looks at the treatment to be treated Surfaces apart from the substances of the formula I also thermosetting resin formers and optionally Catalysts to assist the heat curing of these resin formers applies and then heat-cure. Examples of thermosetting resin formers are used the so-called aminoplast formers into consideration, doh. low molecular weight, N-methylol and substances containing or or N-alkoxymethyl groups. As examples of such Substances that may be mentioned are the polymethylol compounds which are optionally partially or completely etherified of urea, monoalkyl and symmetrical dialkyl ureas, of cyclic ureas, like N, N'-ethylene urea (= imidazolidone-2), N, N'-1,2-propylene urea (= 4-methylimidazolidone-2), N, N -1,3-propylene urea (= N, N'-trimethylene urea or hexahydropyrimidone-2), 5-hydroxyhexahydropyrimidone-2, 4- hydroxy- and 4-alkoxy-5,5-dialkylhexahydropyrimidones, Hexahydro-1, 3-5-triazinon-2- and its 5-alkyl and 5-hydroxyalkyl derivatives, glyoxalmonourein t4,5-dihydroxyimidazolidone-2) and urons, of mono- and dicarbamic acid esters, such as Carbamic acid ethyl ester, carbamic acid propyl-, -butyl-, -ß-hydroxyethyl-, ß-methoxyAthyl- and octyl ester, N-methyl carbamic acid ethyl ester, N-ethyl carbamic acid butyl ester and of dicarbamic acid esters and di-N-ethylcarbamic acid esters of ethylene glycol, 1,3, 1,4-butadiols and 1,6-hexanediols, of aminotriazines such as melamine, ammeline and ammelide, of guanidine, dicyandiamide and dicandiamidine, thiourea and acetylenediurea (= Glyoxaldiurein).

As catalysts to support the heat curing of aminoplast formers acidic and potentially acidic catalysts come into consideration, either strong or medium-strength acids, i.e. acids with a dissosiation constant K. or K1, which is greater than 10-4 4, such as hydrochloric acid, sulfuric acid, phosphoric acid, Oxalic acid, alycolic acid, maleic acid, monochloroacetic acid, trichloroacetic acid, tartaric acid and citric acid, or substances such as esters or especially salts, by themselves from not or very little acid, but by hydrolysis or thermal influence release so much acid that the hardening of the aminoplast formers is accelerated (Under "hardening" in this context is not only the reaction of the aminoplast-forming molecules with each other, but also their reaction with reactive groups of those to be refined To understand the surface). Salts that can be considered as potentially acidic catalysts come, are Z, B. those made of ammonia, amines or polyvalent metals and of medium strength or preferably strong acids, for example ammonium sulfate, ammonium chloride, Ammonium phosphate, ammonium nitrate, di-monoethanolammonium hydrogen phosphate, xthanolammonium chloride, 1-Hydroxy-2-methylpropylammonium-2-chloride, magnesium chloride, aluminum chloride, Zinc chloride, zinc nitrate, zinc fluoborate and zirconyl chloride. Mixtures can also be used several catalysts can be used.

The hardening of the resin formers can, for example, be carried out as usual The effect is that the bodies, the surface of which are the resin formers, the substances of formula I and the catalysts carries, 5 to 15 minutes at a temperature Heated above 1300C, preferably to 14o to 1600C.

Another measure that has proven to be very effective is to the surfaces to be oleophobic apart from the substances of the formula I and optionally to apply water repellants to the resin formers and catalysts. as Water repellants come, for example, paraffin emulsions, stearyl urea and its condensation products with formaldehyde and optionally other aminoplast-forming Substances, stearic acid hydrazide and N-stearyl-N ', N'-ethylene urea into consideration.

The textiles finished in this way are highly oil-repellent and oleophobical is accompanied by hydrophobicity and dirt repellency.

If one intends to take the substances of the formula I from organic solution To apply the fiber material, one leads the disengagement with the thermosetting resin formers and / or the water repellants expediently then in one own work process. But you can also use the substances of the formula I at the same time Apply with the resin formers and / or the water repellants, if one uses the substances of the formula I in the form of aqueous emulsions.

In addition to textiles, the compounds according to the invention can also be used other materials such as wood, paper, leather and plastics have an oil-repellent impregnation or coated.

The parts and percentages given in the examples are weight units.

I. Preparation of bisperfluorocylhydrazine General working instructions 0.1 mol of hydrazine compound A is dissolved in 800 to 900 parts of solvent B. and with stirring at room temperature in the course of 1/2 hour with 0.2 mol of methyl perfluorocarboxylate added drop by drop. In order to end the reaction, you first heat 4 to 5 hours to 40 to 50 ° C. and then stirred for 20 hours at room temperature. The solvent is then stripped off in vacuo and the viscous residue is still briefly dried.

Yield: D's table Example hydrazine compound A solvent B 1 H2N-NH-CH2-CH2-NH2 benzene 2 H2N-NH-CH2-CH2-NH-NH2 methanol CH3 3 NH2-NH-CH-CH2-NH2 methanol 4 H2N-NH- (CH2) 2-NH- (CH2) 2-NH2 benzene 5 H2N-NH- (CH2) 2-NH- (CH2) 3-NH2 benzene 6 NH2-NH- (CH2) 2-NH- (CH2) 2-NH- (CH2) 2-NH- (CH2) 2-NH-NH2 benzene 7 H2N-N-CH2-CH2-NH2 methanol CH2-CH2-NH2 CH3 8 H2N-N-CH-CH2-NH2 methanol CH-CH2-NH2 CH3 Tabel Example end product yield D 1 C7F15-CO-NH-NH-CH2-CH2-NH-CO-C7F15 85% 2 C9F19-CO-NH-NH- (CH2) 2-NH-NH-CO-C9F19 82% CH3 3 C7F15-CO-NH-NH-CH-CH2-NH-COC7F15 96% 4 C7F15-CO-NH-NH- (CH2) 2-NH- (CH2) 2-NH-CO-C7F15 95% 5 C7F15-CO-NH-NH- (CH2) 2-NH- (CH2) 3-NH-CO-C7F15 96% 6 C5F11-CO-NH-NH - [(CH2) 2-NH] -4NH-CO-C5F11 88% 7 C7F15-CO-NH-N-CH2-CH2-NH-CO-C7F15 98% CH2-CH2-NH CH3 8 C7F15-CO-N-CH-CH2-NH-CO-C7F15 97% CH-CH2-NH2 CH3 II. Oleophobic treatment of textile material 10 parts of one of the products of the formula I obtained according to the above information are dissolved in 1000 parts of acetone. The cotton poplin solution is impregnated on a padder at room temperature in such a way that a liquor pick-up of 80% results. Thus, after drying at 80 ° C. and condensation at 150 ° C. (5 minutes), 0.8% of substance remains on the textile material. The fabric finished in this way is good oil-repellent.

A mixture of 10 parts mineral oil with a viscosity of 78 up to 84 c.St. @ (at 500C) and 90 parts of n-heptane is prevented from spreading.

Claims (2)

Claims 1. Perfluorocarboxylic acid derivatives of the general formula in RF a perfluoroalkyl radical with 3 to 11 carbon atoms, R1 a hydrogen atom, a low molecular weight alkyl radical or a radical of the formula -CH2-CH2-NH2 or -CH-CH2-NH2, R2 a CH3 low molecular weight alkylene radical, R3 a hydrogen atom or a low molecular weight alkyl radical , R4 is a low molecular weight alkylene radical, R5 is the radical -O-, -NH- or -NH-NH- and z is zero or an integer from 1 to 3. 2. Use of the substances according to claim 1 as an oil repellent.