Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
  • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
  • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
  • D06M13/21—Halogenated carboxylic acids; Anhydrides, halides or salts thereof
  • D06M13/213—Perfluoroalkyl carboxylic acids; Anhydrides, halides or salts thereof

Definitions

• the invention relates to perfluoroalkyl esters which are suitable for the dirt-repellent finishing of fibers or fabrics made of synthetic or semi-synthetic materials, preferably of polyethylene terephthalate or polyamides.
• perfluoroalkyl or “perfluoroalkoxy” encompasses both those groups with terminal -CF 3 and with terminal -CF 2 H groups.
• lower includes those groups which contain 1 to 4 carbon atoms 10.
• the perfluoroalkyl esters according to the invention are dirt-repellent compounds which have a high repellency to water and oil and which remain on the fiber even after repeated washing and dry cleaning.
• Another advantage of the compounds according to the invention is that they can be applied to the synthetic fiber materials in solution or as a dispersion or can be incorporated by mixing with pellets of the thermoplastic and subsequent shaping into fibers or threads.
• a special advantage of the new dirt-repellent agents is also that they allow the fibers or threads in which these agents are incorporated to be properly dyed.
• the new dirt-repellent agents can also be applied with a dye from a bath with satisfactory results.
• the compounds (1) according to the invention are prepared by reacting a maleic anhydride with 1 mol of a perfluorinated alcohol or alkoxy alcohol of the formula R 1 - (CH 2 ) m OH, optionally in the presence of an inert organic solvent, such as dimethylformamide, N-methylpyrrolidone, hexamethylphosphoric triamide, Tetramethyl urea, toluene, chlorobenzene or dichlorobenzene at temperatures from 30 to 130 ° C, preferably at 40 to 70 ° C.
• This reaction can be carried out by adding a tert.
• Amines like Triethylamine, N, N-dimethylaniline, pyridine, methylpyridines can be accelerated catalytically.
• the maleic acid and / or fumaric acid perfluoroalkyl half esters formed can be converted in a customary manner by reaction with phosphorus chlorides, phosgene or thionyl chloride into the corresponding maleic and / or fumaric acid perfluoroalkyl half esters chloride, which, with suitable alcohols, have the formula appropriate in the presence of proton scavengers such as ter. Amines, to react to the compounds of formula (1).
• the maleic acid and / or fumaric acid-perfluoroalkyl half-esters can, however, also be reacted with epoxides, for example with ethylene oxide, propylene oxide or epichlorohydrin, the ⁇ -hydroxyalkyl esters being formed by opening the oxygen-containing three ring.
• epoxides for example with ethylene oxide, propylene oxide or epichlorohydrin
• This reaction is advantageously carried out with excess epoxide in the presence of an inert organic solvent at temperatures from 30 to 130 ° C., preferably at 40 to 70 ° C.
• the basic esters obtained with amino alcohols such as dimethylaminoethanol, diethylaminoethanol or morpholinoethanol can be reacted further in inert organic solvents with alkylating agents such as dimethyl sulfate, methyl p-toluenesulfonate or alkyl halides to give ammonium alkyl esters.
• alkylating agents such as dimethyl sulfate, methyl p-toluenesulfonate or alkyl halides to give ammonium alkyl esters.
• alkylating agents such as dimethyl sulfate, methyl p-toluenesulfonate or alkyl halides
• alkylating agents such as dimethyl sulfate, methyl p-toluenesulfonate or alkyl halides
• Amines such as triethylamine.
• the compounds of formula (1) according to the invention are suitable for the simultaneous hydrophobization and oleophobicization of synthetic and natural fibers and fabrics, in particular for polyester, polyamide and polyacrylonitrile. These compounds are applied to the textile material by known methods by impregnation with a solution of the compounds of the formula (1) in a suitable organic solvent, preferably in acetone or dimethylformamide. However, the compounds of the formula (1) can also be used in the form of aqueous dispersions. The textile material is squeezed off after impregnation, dried and heat set. The simultaneous use of the compounds of the formula (1) in a conventional fiber preparation agent is particularly preferred.
• the amount of the compounds (1) on the textile material is generally 0.05 to 1, preferably 0.1 to 0.4% by weight of fluorine, calculated from the fluorine content of the compounds of the formula (1) and based on the fiber weight.
• thermoplastics are imparted by the present compounds of formula (1) because of their function of reducing the surface energy of the thermoplastics.
• This effect can be improved by tempering at temperatures above the glass transition temperature of the thermoplastics and below the decomposition temperature of both the thermoplastics and the dirt-repellent. Suitable times for such annealing are in the range of about 5 to 240 minutes. The tempering temperatures are typically around 100 to 220 ° C.
• a further improvement in the effect of the present soil repellants which contain a hydroxyl group in the esterified residue is obtained by using a difunctional or trifunctional epoxide or isocyanate in the liquid medium containing the soil repellent and in which the fiber or other thermoplastic article is incorporated is immersed or sprayed or otherwise treated with a catalyst such as an amine to promote reaction of the hydroxyl group with an epoxy group or isocyanate group upon subsequent annealing.
• the mixture is heated to 50 to 60 ° with stirring and held at this temperature for 7 1/2 hours. According to gas chromatographic determination, after this reaction time the telomer alcohol is used up to a remainder of approx. 2%.
• (102) consists of 90% maleic acid and 10% fumaric acid bis-ester.
• NMR spectroscopy (103) consists of 62% maleic acid and 38% fumaric acid bis-ester.
• the hydrogenation iodine numbers of 40 and 41 g / 100 g correspond to a molecular weight of 627, while a molecular weight of 642.5 is calculated taking into account the composition of the telomer alcohol.
• the cis content is less than 1%.
• the acetone solution of the acid chloride from Example 18 was mixed with the same amount of water and the calculated amount of pyridine and stirred for 4 hours at room temperature. After acidification with hydrochloric acid (1: 1), a beige precipitate was obtained, which was stirred, suction filtered, washed free of Cl ions and dried at 60 ° in vacuo. The titration provides good values for the expected equivalent weight.
• the alcohol was (if miscible with water, possibly in a 100% excess) in acetone with the calculated
• the amount of pyridine is initially charged and an acetone solution of the acid chloride from Example 18 is added dropwise.
• the reaction mixture was refluxed for 3 hours, the solvent was distilled off, the remaining, mostly resinous residue was stirred several times with water (from 50 °) until no more Cl ions were detectable and dried at 50 ° in vacuo. If separation from the aqueous phase proved difficult, the resinous reaction product was taken up in ethyl acetate, washed with water free of ions, dried and evaporated.
• the half ester from Example 16 was dissolved in dimethylformamide, the equimolar amount of glycidyl-trimethyl-ammonium chloride was added at 54 ° and the mixture was stirred at this temperature for 24 hours. After cooling to 20 °, the product was filtered off with suction, the filter cake was washed with dimethylformamide and the reaction product was precipitated in the filtrate with toluene. The mixture was stirred at 50 °, decanted, washed with toluene and dried at 50 ° in vacuo.
• a polyamide fabric was impregnated under the same conditions as indicated above with a liquor consisting of a solution of 5 g of compound (104) from Example 4 in 1 liter of acetone.
• the heat setting was carried out here at 190 ° C. for 5 minutes.
• the value 5 was measured here for the oil repellency effect according to AATCC No. 118-1966. After washing five times at 40 ° C, the value was still 4.
• the compounds listed below were applied to a fabric made of polyamide 6 filaments and polyester using a padding machine with a liquor absorption of 40-50%.
• the amount of product was chosen so that about 0.125% circulation There is fluorine on the fabrics after drying.
• the work was carried out from acetone solutions which contained approximately 1.2 g of substance in 250 ml of acetone.
• the following compounds according to the invention were used:
• the fabrics were air dried once, once condensed at 160 ° C for 1 minute and once at 160 ° G for 30 minutes.
• the oil repellency values according to AATCC were checked directly (AN) and after 3 x washing at cooking temperature (3 x kW) in a washing machine.

Landscapes

• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Epoxy Compounds (AREA)

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Publications (2)

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• 1982
  • 1982-08-27 US US06/412,127 patent/US4473371A/en not_active Expired - Fee Related
  • 1982-08-31 EP EP82107984A patent/EP0074057A3/fr not_active Withdrawn
  • 1982-09-02 ES ES515453A patent/ES8306091A1/es not_active Expired
  • 1982-09-03 AU AU87978/82A patent/AU8797882A/en not_active Abandoned
  • 1982-09-03 BR BR8205212A patent/BR8205212A/pt unknown

Patent Citations (3)

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