DE2065040A1 - Polymers of 5-(3-perfluoroalkyl 1,2,4-oxa-diazolyl) alkenes - Google Patents

Abstract

These are prepared by (co)polymerising monomers of formula: where m = 1-18, R1 is -CH=CH2 or -C(CH3)=CH2 and R2 is an ethylenically unsaturated hydrocarbon residue derived from fumaric, maleic citraconic, mesaconic or itaconic acid. Alkyl vinyl ethers are preferred comonomers. Certain intermediates in the preparation of I, of formula (CmF2m+1-C=N-O-CO)-2 R2, are new compounds.The polymers confer oil- and water-repellency on textiles, leather, paper, wood, brickwork, metals, synthetics, glass and painted surfaces. The dye receptivity of synthetic polymers, especially of polyolefines, is improved by addition of the polymers

Description

Fluorinated O-substituted amidoximes The present invention relates to new monomers containing perfluoroalkyl groups, the homopolymers and copolymers which can be prepared therefrom, processes for producing these polymers, their use for making materials such as textiles in particular dirt-repellent, and mixtures of such homopolymers and copolymers together and / or with others Polymers, The new monomer compounds of the present invention are 5- (3-perfluoroalkyl-1,2,4-oxadiazolyl) -ethylenes and we correspond to the formula I: in which formulas m is an integer from 1 to 1S, preferably 3 to 7, and in particular 7, R1 in particular —CH = CH2, and R2 represents an ethylenically unsaturated hydrocarbon radical derived from fumaric acid, maleic acid, citraconic acid, mesaconic acid or itaconic acid, in particular from fumaric acid.

These monomer compounds of the formulas 1 and II are obtained by means of known processes, for example as described by HC Brown and CR Wetze1 i: l J.Org.Chem. 30, 3734 (1965). In both cases of the preparation of the compounds of the formulas I and II, the fluorinated O-substituted amidoximes used as starting material can be prepared in a known manner, for example as described in British Patent 1,178,891, according to the following reaction: For the monomers of Formula I: For the monomers of formula II: In these reaction formulas, R1, R2 and m have the meanings given under formulas I and II, and Y is halogen, such as chlorine or bromine.

The compounds of the formula mentioned in the reaction sequence for the preparation of the monomers of the formula II in which m and R2 have the meanings given above are new.

The condensation reaction is caused by the amidoxime and reacting the acyl halide together.

This reaction is expediently carried out in a solvent by, suitably in dry acetonitrile and while stirring the reaction mixture for about 1 hour to 12 hours at a temperature of about 25OC to 85CC, to ensure the highest yields. By subsequent evaporation of the The desired product is obtained using a solvent. If desired, this can be done through Recrystallization from a hydrocarbon solvent such as petroleum ether mixed with a ketone, for example Acetone, or an ester such as ethyl acetate getting cleaned.

The starting materials for the O-substituted amidoximes are light obtainable or can be prepared by known methods. For example is the preparation of perfluoroacylamidoximes by Brown and Wetzel in J.Org.Chem., 30, 3734 (1965). The acyl halides are or may be items of commerce be prepared in a known manner.

Subsequently, the O-Acylperfluoracylamidöxime are then by reacting with cyclizing agent or by thermal dehydration the monomer compounds of formulas I and II. Examples of O-acylperfluoroacylamidoximes, the Particularly useful in the practice of the present invention are O-methacrylic perfluorooctane amide oxime, O-methacrylacetamidoxime, O-fumaryl-bis- (n-perfluorobutyramidoxime) and in particular O-fumarylbis (n-perfluorooctane amide oxime).

Examples of cyclizing agents which are used for the ring closure of the above O-acylperfluoroacylamidoximes mentioned are phosphorus pentoxide and formamidine or s-triazine.

The thermal dehydration is done by heating the amidoximes in a distillation flask with a direct flame at normal pressure or in a vacuum causes.

Preferred monomer compounds are 1,2-bis-t5- (3-n-per £ 1uorheptyl-1,2,4-oxadiazolyl)] ethylene and 5-isopropenyl-3-n-pereluoroheptyl-1,2,4-oxadiazole.

As indicated in the formulas above, perfluoro groups having 1 to 18 carbon atoms can be used, and it is understood that mixtures of compounds with perfluoro groups with different numbers of carbon atoms can be used within the range given above. Both straight chain as well as branched perfluoroalkyl groups are included.

The corresponding polymers obtainable from the monomers are those which have skeletal chains, the repeating units of the formulas contain, where m has the meaning given under formula I and R1, -CH2-CH2- or and R2 'is a hydrocarbon radical derived from fumaric acid, maleic acid, citraconic acid, mesaconic acid or itaconic acid.

In addition to the homopolymers, the polymers according to the invention include the new fluoromonomers of the formulas I and II are copolymers with others Ethylenically unsaturated monomers and physical mixtures of such Homopolymers and copolymers together and / or with other polymers.

Because the new homopolymers and copolymers are mainly used as textile finishes Find use, it is often desirable to add about 0.2 to Incorporate 5 percent by weight of a reactive acrylic comonomer, the crosslinking either by heating or by crosslinking agents.

Such reactive fluorine copolymers result in textile finishes with superior resistance to washing, dry cleaning, the chafing, the wear and the scuffing, both in the dry and in the wet condition, and there is better durability of the oil and water repellent Properties.

The polymerization of the monomers of the formula I or II can be carried out in the Bulk, in solution or emulsion. The preferred polymerization techniques are emulsion polymerization in an aqueous medium and solution polymerization.

The polymerization temperature depends on the catalyst chosen away.

In the case of emulsion polymerization, the one or those to be polymerized Monomers preferably together with a solvent such as acetone in an aqueous solution Surfactant solution to a given concentration of monomers emulsified from about 5 to 50%. In general, the temperature will be between 70 and 100 ° C increased to effect the polymerization in the presence of an added catalyst. A suitable catalyst can be any of the well-known water-soluble agents be to initiate the polymerization of an ethylenically unsaturated compound. The concentration of the catalyst for the polymerization is generally between 0.1 to 2% based on the weight of the monomers.

Suitable surfactants or emulsifiers include cationic, anionic or non-ionic types.

As the cationic types are used in most textile treatment baths they are preferred. The hydrophobic part of the surfactant can be a hydrocarbon or a fluorinated hydrocarbon.

Suitable cationic surfactants include, for example quaternary ammonium salts or amine salts which contain at least one long-chain alkyl, Fluoroalkyl or highly alkylated benzene or naphthalene groups containing the represent hydrophobic portion.

Suitable surfactants are also non-ionic surfactants Agents in which the hydrophilic group is a poly (ethoxy) group and the hydrophobic group Is part of either a hydrocarbon or a fluorocarbon group, like the ethylene oxide condensates of alkylphenols, alkanols, alkylamines, alkylthiols, Alkyl carboxylic acids, fluoroalkyl carboxylic acids, fluoroalkylamides and the like.

The polymerization is preferably carried out during a reaction period carried out, achieved in which substantially a quantitative conversion of the monomers will. The optimal reaction time depends on the catalyst used and the polymerization temperature and other conditions, but generally lies in the area from 0.5 to 24 hours.

The polymerization is preferably carried out at atmospheric pressure.

In the solution polymerization, the monomer or monomers in one suitable solvents, such as fluorinated solvents, for example fluorine halogenated hydrocarbons, such as hexafluoroxylene, trifluorotoluene or Mixtures thereof with acetone and / or ethyl acetate, in other fluorinated solvents and the like, and then in a polymerization vessel using initiators, such as azobisisobutyronitrile, benzoyl peroxide or tert. Butyl perbenzoate, at concentrations polymerized from 0.1 to 2.0% at 70 to 140 "C under nitrogen.

As mentioned at the outset, valuable copolymers are used in addition to homopolymers obtained by polymerizing the above-mentioned new perfluorinated monomers of the formulas I and II with other polymerizable monomers, the ethylenic Show unsaturation.

The monomers of the formula I show a copolymerization behavior, which is similar to that of the acrylate and methacrylate monomers. Suitable comonomers for this are described in detail by C.E. Schildknecht in 'Vinyl and related Polymers' Pages 179 to 255 (John Wiley & Sons, Inc., New York 1952). From these comonomers In particular, the esters of acrylic and methacrylic acid with alkyl ester groups come from 1 to 18 carbon atoms, such as methyl, ethyl, isopropyl, n-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-dodecyl, n-octadecyl acrylate and methacrylate into consideration.

The monomers of the formula II show a copolymerization behavior, which is similar to that of fumarates and maleates. Examples of suitable comonomers for monomers of the formula II are: a) alkyl vinyl ethers, such as methyl vinyl ether, isopropyl vinyl ether, Isobutyl vinyl ether, 2-methoxyethyl vinyl ether, n-propyl vinyl ether, tert. Butyl vinyl ether, Isoamyl vinyl ether, n-hexyl vinyl ether, 2-ethylbutyl vinyl ether, diisopropylmethyl vinyl ether, Isomethylheptyl vinyl ether, n-decyl vinyl ether, n-tetradecyl vinyl ether and n-octadecyl vinyl ether, but especially methyl vinyl ether, Ethyl vinyl ether, n-propyl vinyl ether, Isopropyl vinyl ether, 2-methoxyethyl vinyl ether and 2-chloroethyl vinyl ether.

Vinyl comonomers with short side chains are preferred.

b) «-olefins, such as propylene, butyn and especially isobutylene.

Straight-chain and straight-chain α-olefins with up to 18 Carbon atoms in the side chain into consideration.

c) vinyl esters, e.g. vinyl acetate, vinyl esters of substituted acids, such as vinyl methoxy acetate, vinyl trimethyl acetate, vinyl isobutyrate, isopropenyl butyrate, Vinyl lactate, vinyl caprylate, vinyl pelargonate, vinyl miristate, vinyl oleate and vinyl linoleate; Vinyl esters of aromatic acids such as vinyl benzoate and vinyl alkoxybenzoates, in particular but vinyl acetate, vinyl propionate, vinyl benzoate and isopropenyl acetate.

d) styrene and related monomers, such as -methylstyrene, p-methylstyrene, 3,4-dimethylstyrene, 2,4,6-trimethylstyrene, m-ethylstyrene, 2,5-diethylstyrene.

e) Additional usable comonomers are ethylene and chlorine, fluorine and cyan derivatives of ethylene, such as vinyl chloride, vinylidene chloride, vinyl fluoride, Vinylidene fluoride, acrylonitrile, methacrylonitrile, tetrafluoroethylene, trifluorochloroethylene, Hexafluoropropylene, acrylate and methacrylate monomers, especially those with 1 to 18 carbon atoms in the ester groups, such as n-propyl methacrylate, methyl methacrylate, tert. Butyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, Butyl acrylate, octyl acrylate, tetradecyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, 2-methoxyethyl acrylate and phenyl acrylate; Serves, especially 1,3-butadiene, isoprene and chloroprene, 2-fluorobutadiene, 1,1,3-trifluorobutadiene, 1,1,2,3-tetrafluorobutadiene, 1,1,2-trifluoro-3,4-dichlorobutadiene and tri- and pentafluorobutadiene and isoprene; Nitrogen vinyl monomers such as vinyl pyridine, N-vinyl imides, amides and secondary cyclics Amines such as vinyl succinimide, vinyl pyrrolidone, N-vinyl carbazole, and the like.

Vinyl monomers, the perfluorinated side chains, are also suitable contain. Examples of such perfluorinated monomers are vinyl ethers of the type as described in U.S. Patents 2,732,370 and 2,828,025; Vinyl ester, containing fluorinated alkyl groups described in U.S. Patents 2,592,069 and 2,436,144 are described. Other useful monomers are acrylates and methacrylates and derivatives thereof, such as those described in U.S. Patents 2,628,958, 3,256,230, 2,839,513, 3,282,905, 3,252,932 and 3,304,278 are described.

As already mentioned at the beginning, it can also be desirable to include a small amount of other reactive comonomers in order to reduce the washing and to improve the dry cleaning properties of the new textile finishes that can be obtained using the present invention. Such comonomers act as crosslinking agents during the curing process. Such reactive comonomers are generally used in amounts of 0.1 to 2%. Let me explain reactive comonomers mentioned that can be incorporated: acrylic acid, methacrylic acid, Acrylamide, methacrylamide, N-methylolacrylamide, 2-hydroxyethyl methacrylate or acrylate, Hydroxypropyl acrylate or methacrylate and tert. Butylaminoethyl methacrylate or Glycidyl methylate, especially N-methylolacrylamide and 2-hydroxyethyl methacrylate.

It is also beneficial, especially in the manufacture of Fabric finishes, mixtures of emulsions or solutions of other polymers to use. Such mixtures serve to essentially provide the amount of the required fluorinated polymer to reduce economically acceptable repellency properties to achieve and to give the fabrics a softer feel than if only one would use the more brittle fluorinated polymers alone.

Examples of such other polymers are non-fluorinated ones Polymers into consideration, for example polymers and copolymers of Alkyl acrylates and alkyl methacrylates, such as methyl methacrylate, ethyl methacrylate, liexyl methacrylate and n-octyl methacrylate. A particularly suitable polymer is Poly (n-octyl methacrylate).

Polymers and copolymers of acrylic acid can also be used, Methacrylic acid, styrene, alkyl styrene, butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene; Polymers and copolymers of vinyl ester, such as vinyl acetate, vinyl butyrate, Vinyl laurate, vinyl stearate, vinyl 2-ethylhexanoate; Polymers and copolymers of vinyl halides and vinylidene halides, such as vinyl chloride, vinylidene chloride, Vinyl fluoride, vinylidene fluoride; Polymers and copolymers of allyl ester, such as allyl propionate or allyl caprylate; Polymers and copolymers of vinyl ketones, such as vinyl methyl ketone, vinyl ethyl ketone and the like; Polymers and copolymers vinyl ethers such as methyl vinyl ether, cetyl vinyl ether and the like; Polymers and copolymers of acrylamide, methacrylamide, N-methylolacrylamide, N-methylol methacrylamide, N-isopropyl acrylamide, and acrylonitrile and methacrylonitrile.

For example, mixtures provide from 20 to 97 percent by weight of one Homopolymer of poly (n-octyl methacrylate) with the polymers according to the invention very useful coating compositions that have surprisingly high repellency ratings retain, although the relative amount of the inventive perfluorinated polymers is relatively low.

These polymers and these mixtures produce oil and water repellants Finishes that are used to treat materials, especially textiles Leather, paper, wood, masonry, metals, plastics, glass, painted surfaces and the like are suitable.

The coatings with the homo- and copolymers according to the invention can be prepared and applied from solvent solutions or from aqueous emulsions will. Suitable solvents are fluoroalkanes, fluorochloroalkanes, fluoroalkyl-substituted ones Aromatics, alkyl esters of perfluoroalkanecarboxylic acids, chlorinated alkanes or aromatics, Hydrocarbon aromatics, ketones, esters and ethers. Particularly useful as a solvent are fluorinated liquids, and in particular benzotrifluoride and hexafluoroxylene and mixtures of these with ethyl acetate or acetone and the like. The concentrations the according to the invention fluorinated polymers in the solvents are generally in the range from 0.01 to 10% and preferably from 0.1 to 2.0 Weight percent.

The coatings can be easily applied by various means coating processes known to the person skilled in the art, such as dipping, spraying, brushing, Padding, roller application and the like.

For evaluation purposes, the fabric in the following examples was used immersed in a bath containing the polymer to be evaluated and the amount the retained solution adjusted so that about 2% of the polymer, based to the weight of the fabric on which the fabric remained. The tissue is at room temperature dried and in an oven at a temperature of about 1750C for about 2 minutes hardened.

The type of fabric that is covered is not critical. For evaluation purposes, reject ratings were determined for cotton or wool as a standard test method, but fibers such as those made of fiberglass, Silk, regenerated cellulose, cellulose esters and ethers, polyamides, polyesters, Polyacrylonitrile, polyacrylates and other fibers, alone or mixed or in Combination with the inventive polymers are coated.

Another embodiment of the present invention is based on the finding that these new polymers are difficult to color organic materials, such as polyolefins of the polyethylene and polypropylene types, dyeing make it more accessible. Homopolymers and copolymers are particularly effective for this purpose of 5-isopropenyl-3-n-perfluoroheptyl-1,2,4-oxadiazole and trans-1,2-bis- [5- (3-perfluoroheptyl-1,2,4-oxadiazolyl)] ethylene.

The polymers according to the invention can be used in those which are difficult to color organic matter can be incorporated during normal machining operations. For example, they can be incorporated into polypropylene by pickling; The polymers can then be extruded, pressed, blow molded or in formed in another way into films, fibers, filaments, hollow bodies and the like will. The new compositions can then either directly after compounding or after further treatment, such as after the formation of yarns or fabrics, to be colored.

Generally about 0.05 to 10 weight percent and preferred about 0.1 to 6 percent by weight of the polymers according to the invention in the difficult used to be colored organic material. However, the amount is not critical.

The conditions for dyeing vary with the dye used. In general, the kind of the dye is not limited, and any of known acidic, substantive and metallized dyes are used.

In addition to the poly-α-olefins, the polymers can also be used in others Substances used for the same purpose, their regular and inert chemical Structures tend to withstand the dyes. Materials for which the Compounds according to the invention which are useful therefore include: synthetic organic polymeric substances, both homopolymers and copolymers, such as vinyl resins, poly-a-olefins, polyurethanes, polyamides, polyester, polycarbonate, Polyacetals, polystyrene, polyacrylic acids and the like.

In the following examples, the repellency ratings were as follows Determined: The AATCC water spray test rating was according to the standard test method 22-1966 of the American Association of Textile Chemists and Colorists, XXXVII, 1961, Page 1952 (also referred to as ASTM-D 583-58).

The oil repellency was determined by the 3-M oil test method from Grajek and Peterson, Textile Research Journal, Apr. 1962, p. 323.

The following examples serve to further illustrate the present Invention. Unless otherwise stated, parts by weight are related to parts by volume like g to cm3.

Example 1 5-Isopropenyl-3-n-perfluoroheptyl-1,2,4-oxadiazole A. O-Methacrylyl perfluorooctane amide oxime Perfluorooctane amide oxime [prepared according to H.C. Brown and C.R.

Wetzel, J. Org. Chem., 30, 3734 (1965); 27 g, 0.063 mol @ becomes fine powdered and suspended in dry acetonitrile (140 ml).

This suspension is added dropwise with vigorous stirring Room temperature a solution of methacrylyl chloride (6.6 g 0.063 mol) in 14 ml dry Acetonitrile. The mixture is stirred at room temperature for 2 hours and 2 additional hours Refluxed for hours. Removal of the solvent under reduced Pressure gives a crystalline product which, after recrystallization from acetone hexane 27 g (86%) of O-methacrylyl perfluorooctane amide oxime with a melting point of 132.5 to 137 ° C. results.

The NMR spectrum (acetone-d6) shows a double at 2.00 cr (CH3), two multiplets at 5.71 and 6.24 for the vinylic protons and one broad signal at 6.97 for the -NH2 protons.

The infrared spectrum shows absorptions at 2.8 to 3.0 µ (NH2), 5? 75 (= 0), 6.0 (C = N) and 6.2 (C = C).

Analysis C12F19H7N202: Calculated C 29.04 H 1.42 found C 29.24 H 1.36.

If, in the above example, instead of perfluorooctane amide oxime, perfluorobutyramido oxime, Perfluorododecanamide oxime or perfluorononadecynamidoxime and instead of methacrylyl chloride If acrylyl chloride are used, O-acrylyl perfluorobutyramidoxime, O-acrylylperfluorododecanamide oxime is obtained or O-acrylyl perfluorononadec anamidoxime B. 5-isopropenyl-3-n-perfluoroheptyl-1,2,4-oxadiazole O-Methacrylylperfluorooctanamidoxim (0.054 mol) is with an excess of phosphorus pentoxide (0.35 mol) intimately mixed and placed in a distillation flask with connected to an ice-cold trap. The piston is then operated with a direct Flame heated and subjected to an initial vacuum of 1 mm Hg. The reaction is fast and when they once started, it runs without further ado Warm up. The yield of the crude product is 7.0 g (boiling point 630C at 0.09 mm Hg pressure).

The NMR spectrum shows a singlet at 1.8 .r for the methyl protons and two nultiplets at 5.3 and 5.9 for the vinyl protons.

If in the above example instead of O-methacrylyl perfluorooctane amide oxime O-acrylyl perfluorobutyramidoxime, O-acrylylperfluorododecanamidoxime or O-acrylylperfluorononadecanamidoxime 5-vinyl-3-n-perfluoropropyl-1,2,4-oxadiazole, 5-vinyl-3-n-perfluorundecyl-1,2,4-oxadiazole are obtained and 5-vinyl-3-n-perfluorooctadecyl-1,2,4-oxadiazole, respectively.

Example 2 Trans-1,2-bis [5- (3-n-perfluoroheptyl-1,2,4-oxadiazolyl)] ethylene.

A. O-Fumaryl-bis- (n-perfluorooctane amide oxime) Add 3.2 g (0.0209 Mol) fumaric chloride in 20 ml of spectrally pure acetonitrile dropwise to a stirred Mixture of n-perfluorooctane amide oxime [H.C. Brown and C.R. Wetzel, J.Org.Chem., 30, 3734 (1965)] (19 g, 0.044 mol) in 80 ml acetonitrile. The reaction mixture is then Boiled gently for 90 minutes while allowing a stream of nitrogen through the reaction vessel conducts to remove the hydrogen chloride formed. The product is filtered and dried to give 19.5 g of O-fumaryl-bis- (n-perfluorooctane amide oxime) of melting point 2660C (dec.).

Analysis C20El 6F30N404 calculated: C 25.65 H 0.64 F 60.87 N 5.98 found: C 25.79 H 0.60 F 61.40 N 5.85 when in the above example instead of fumaric chloride Citraconyl chloride, mesaconyl chloride or itaconyl chloride can be used O-citraconyl-, O-mesaconyl- or O-itaconyl-bis- (nperfluorooctane amide oxime).

B. Trans-1,2-bis- [5- (3-n-perfluoroheptyl-1,2,4-oxadiazolyl)] ethylene 3.0 g of O-fumaryl-bis (n-perfluorooctane amide oxime) are added. into a round bottom flask and heated with a direct flame until the Melted whole is. The subsequently cooled reaction mixture is recrystallized from chloroform. 2.3 g of a yellow product with a melting point of 83 to 840 ° C. are obtained. The W spectrum (Methanol) has absorptions at N 278 and # 268.5 mµ with an extinction coefficient from 12600 or 13800.

Analysis C20H2F30N403 calculated: C 26.88 H 0.22 F 63.31 N 6.22 found: C 26.99 I 0.17 F 63.27 N 7.72.

If in the above example instead of O-fumaryl-bis- (n-perfluorooctanamide oxime) O-citraconyl-, O-mesaconyl- or O-itaconylbis- (n-perfluorooctane amide oxime) are used cis- and trans-1,2-bis- [5- (3-n-perfluoroheptyl-1,2,4-oxadiazolyl)] propene are obtained and 2,3-bis- [5- (3-perfluoroheptyl-1,2,4-oxadiazolyl)] propene.

Example -3 Trans-1,2-bis- [5- (3-n-perfluoropropyl-1,2,4-oxadiazolyl)] ethylene A. O-fumaryl-bis- (n-perfluorobutyramidoxime) This compound is obtained from fumaryl chloride and n-perfluorobutyramidoxime according to the procedure of Part A of Example 2.

The yield is 87% and the product melts below 277 ° C Decomposition.

Analysis C12H6F14N404 calculated: C 26.87 H 1.12 F 49.60 N 10.44 found: C 27.00 H 1.12 F 49.55 N 10.53.

If in the above example instead of n-Perfluorobutyramidoxim n-Perfluordodecanamidoxim or n-Perfluornonadec anamidoxim are used, one obtains O-Fumaryl-bis- (n-Perfluordodecanamidoxim) or O-fumaryl-bis- (n-perfluorononadecanamide oxime).

B. Trans-1,2-bis- [5- (3-n-perfluoropropyl-1,2,4-oxadiazolyl)] ethylene The dehydration of O-fumaryl-bis- (n-perfluorobutyramidoxime) according to A was carried out, as described in Part B of Example 2. The product obtained is made from Recrystallized petroleum ether. It has a melting point of 62 to 65 ° C.

If in the above example instead of O-fumaryl-bis- (n-perfluorobutyramidoxime) O-fumaryl-bis- (n-perfluorododecanamidoxime) or O-fumaryl-bis- (n-perfluoronadecanamidoxime) is used, trans-1,2-bis- [5- (3-n-perfluorundecyl-1,2,4-oxadiazolyl)] ethylene is obtained or trans-1,2-bis [5- (3-n-perfluorooctadecyl-1, 2,4-oxadiazolyl)] ethylene.

Example 4 100 parts of a mixture of 5-isopropenyl-3-n-perfluoroheptyl-1, S, 4-oxadiazole, produced according to Example 1, n-octyl methacrylate, according to the following table I and 1 part of azobisisobutyronitrile are melted in an ampoule under nitrogen and polymerized at 80 ° C for 16 hours. The polymer is then in 500 Parts of benzotrifluoride dissolved and precipitated in 20 times the amount of methanol. the Homopolymers and copolymers turn out to be fine white after high vacuum drying Powder received. The mixed polymer composition and the repellency ratings, which are obtained, determined by applying 2 percent by weight of the new polymers on the tissue from a benzotrifluoride solution are shown in Table I below specified.

Table I. 5-isopropenyl-3-n-n-octylmeth repulsion (2% polymer perfluoroheptyl acrylate on the fabric) at 1,2,4-oxadiazole play weight dyn Weight%% cm tissue 3-M oil AATCC water 4a 100 0 11.5 cotton 90 90 Wool 80 80 4b 88.5 11.5 - cotton 80 80 Wool 70 90 4c 78.8 21.2 - cotton 70 80 Wool 70 90 4d 54.0 46.0 - cotton 60 70 Wool 60 90 If, in the above example, instead of 5-isopropenyl-3-n-perfluoroheptyl-1,2,4-oxadiazole, 5-vinyl-3-n-perfluoropropyl-1,2,4-oxadiazole, 5-vinyl-3-n-perfluorundecyl-1 , 2,4-oxadiazole or 5-vinyl-3-n-perfluorooctadecyl-1,2,4-oxadiazole and, instead of n-octyl methacrylate, 2-ethylhexyl acrylate are used, homopolymers and copolymers with improved repellency ratings are obtained.

Example 5 2% solutions of the mixtures of the homopolymers of 5-isopropenyl-3-n.perfluoroheptyl-1,2,4-oxadiazole and poly (n-octyl methacrylate) in various mixing ratios according to Table II below are applied to the fabric and the rejection ratings as determined in the previous examples. The results are given in Table II. Table II Composition of the mixture repulsion (2% polymer on the fabric) 5-isopropenyl poly (n-octyl At- 3-n-perfluoromethacrylate game heptyl-1,2,4- Tissue 3-M oil AATCC water oxadiazole Weight% weight% 5a 100 0 cotton 90 90 Wool 80 5b 60 40 cotton 80 80 Wool 80 80 5c 40 60 cotton 80 80 Wool 80 80 5d 20 80 cotton 80 70 Wool 80 70 5e 10 90 cotton 70 70 Wool 80 70 5f 5 95 cotton 60 70 Wool 80 70 If, in the above example, ethylene-propylene terpolymers or butadiene-styrene copolymers are used instead of poly (n-octyl methacrylate), mixtures with improved repellency ratings are obtained.

Example 6 100 parts of a mixture of equimolar amounts of trans-1,2-bis- [5- (3-n-perfluoroheptyl-1,2,4-oxadiazolyl)] ethylene, hergestell.t according to Example 2, and a vinyl ether according to the following table III, column 2, 400 parts of ethyl acetate and 1 part of azobisisobutyronitrile are in an ampoule melted under nitrogen and polymerized for 16 hours at 80.degree. The resulting copolymer, which precipitates out during the polymerization reaction, is dissolved in 900 parts of hexasfluoxylene, and the polymer solution with 20 times Amount of methanol precipitated.

The precipitated and dried polymer: e, white to weak yellow powders, or sticky materials, are obtained in pouches exceeding 80%.

The copolymers obtained are applied to the fabric from a 2-strength solution in hexafluoroxylene in order to provide a coating which represents 2 percent by weight of polymer on the fabric. The repellency ratings are determined as described above and are given in Table III below. Table III Appearance of the repulsion (2% polymer on At- Vinyl ether mixed polymer fabric) game merisats tissue 3-M oil AATCC water 6a CH2 = CHOCH3 yellow-white cotton 100 80 Powder wool 120 80 6b CH2 = CHOC2H5 yellow and white sticky cotton 100 70 Polymer wool 110 70 6c CH2 = CHOCH2CH (CH3) 2 yellow sticky cotton 90 70 Polymer wool 100 70 6d CH2 = CHOCH2CH2OCH3 yellow sticky cotton 100 70 Polymer wool 100 70 6e CH2 = CHOCH2CF3 yellow powder cotton 100 70 Wool 110 70 If in the above example instead of trans-1,2-bis- [5- (3-n-perfluoroheptyl-1,2,4-oxadiazolyl)] -ethylene cis- or trans-1,2-bis [5- (3-n -perfluoroheptyl-1,2,4-oxadiazolyl)] propene or 2,3-bis [5- (3-n-perfluoroheptyl-1,2,4-oxadiazolyl)] propene and styrene can be used instead of vinyl ether, see above mixed polymers are obtained which show increased rejection ratings.

Example 7 100 parts of a mixture of equimolar amounts of trans-1,2-bis- [5- (3-n-perfluoropropyl-1,2,4-oxadiazolyl)] ethylene, prepared according to Example 3, and methyl vinyl ether, 300 parts of ethyl acetate and 1 part of azobisisobutyronitrile is melted in an ampoule under nitrogen and polymerized at 70 ° C for 16 hours. After the polymerization, the polymer solution is diluted with 600 parts of ethyl acetate and precipitated in 20 times the amount of methanol. After drying, the mixed polymer is obtained as a fine yellowish white Powder with a melting point of 93 to 102 ° C.

The critical surface free energy of a polymer film, determined by contact angle measurements, as in Advances in Chemistry, Series 43, pages 1 through 49; A.C.S. (1964) is 12 dynes / cm. Copolymers with: critical Surface free energies below 12 dynes / cm can be obtained if- im Example above trans-1,2-bis [5- (3-n-perfluoropropyl-1,2,4-oxadiazolyl)] ethylene by trans-1,2-bis- [5- (3-n-perfluorundecane-1,2,4-oxadiazolyl) 1-ethylene or trans-1,2-bis- [5- (3-n-perfluorooctadecane-1 , 2,4-oxadiazolyl)] - ethylene is replaced,

Claims (4)

Claims 1. Compounds of the formula where m is an integer from 1 to 18 and R2 is an ethylenically unsaturated radical derived from fumaric acid, maleic acid, citraconic acid, mesaconic acid or itaconic acid. 2. Compounds according to claim 1, characterized in that m 3 to 7 means. 3. O-fumaryl-bis- (n-perfluorooctane amide oxime). 4. Use of the compounds of claims 1 to 3 as intermediates for the production of 5- (3-perfluoroalkyl-1,2,4-oxadiazolyl) olefins.