Patent GB-933512-A (GB)
Title: Textile treating agents
Inventor: LANGERAK ESLEY OREN
IPC: C08F220/22
Filed: 1961-10-17
Abstract: Interpolymers of N-methylol acrylamide compounds of formula Q-NH-CH2OH where Q is the acyl radical of acrylic or methacrylic acid, with at least one fluoroalkyl ester of formula Q-OCH2(CF2-CF2)mH where m is 1 to 6, or Q-OCH2(CF2)nF or Q-OCH2CH2(CF2)nF where n is 2 to 12, said N-methylol acrylamide constituting not less than 0,25% and not more than 5% by weight of the interpolymer, may be prepared by copolymerizing the monomers in aqueous emulsion in the presence of free radical generating catalysts.  Suitable catalysts are hydrogen peroxide, benzoyl peroxide, potassium persulphate, 2,21-azodiisobutyramidine dihydrochloride and redox systems comprising potassium persulphate and sodium bisulphite. Emulsifiers, e.g. sodium lauryl sulphate, ammonium di1H,1H,7H-dodecafluoroheptyl) phosphate and octadecyltrimethyl ammonium chloride or bromide, and buffers, e.g. sodium borate, may be present.  Many suitable fluoralkyl esters are listed and examples describe the preparation of interpolymers of N-methylol acrylamide or methacrylamide with (2) 1H,1H-pentadecafluorooctyl acrylate, (3) 1H,1H-nonadecafluorodecyl acrylate, (4, 6 and 8) 1H,1H,11H-eicosafluorohendecyl and 1H,1H,7H-dodecafluoroheptyl acrylates, (5 and 9) 1H,1H,11H-eicosafluorohendecyl and 1H,1H,5H-octafluoropentyl acrylates or methacrylates, (7) 1H,1H,9H-hexadecafluorononyl acrylate or methacrylate, (10) 1H,1H-pentafluoropropyl acrylate or methacrylate, (11) 1H,1H,9H-hexadecafluorononyl and 1H,1H-pentafluoropropyl acrylates, and (12) 1H,1H,2H,2H-tridecafluorooctyl methacrylate; and (13) interpolymers of N-methylol acrylamide with a mixture of methacrylates of formula F(CF2)nCH2CH2O.CO.C(CH3)=CH2 where n is 6, 8 and 10.  Aqueous dispersions of the polymers may be applied to textile fabrics, paper and regenerated cellulose sheets, dried and cured by heating to impart water- and oil-repellency thereto.  In Example 14 strips of regenerated cellulose film are padded with aqueous dispersions of copolymers of 1H,1H,9H-hexadecafluorononyl acrylate, 1H,1H-pentafluoropropyl acrylate and N-methylol acrylamide. Specifications 703,434 and 703,435 are referred to.ALSO:1H,2H,2H-iodopolyfluoroalkyl acetates may be prepared by reacting vinyl acetate with 1-iodopolyfluoroalkanes in the presence of azodiisobutyronitrile. 1H,1H,2H,2H-polyfluoro-1-alkanols may be prepared by reducing the above product with an alcoholic slurry of zinc dust and concentrated hydrochloric acid, and hydrolysing the product with an alcoholic solution of potassium hydroxide.  In example (1) vinyl acetate is reacted with 1-iodopentadecafluoroheptane to give 1H,2H, 2H-iodopentadecafluorononyl acetate, which is reduced and hydrolysed to give 1H,1H, 2H,2H-pentadecafluoro-1-nonanol. Specifications 703,434 and 703,435 are referred to.ALSO:Textile fabrics, e.g. of cotton, wool, nylon or polyester, are rendered oil and water repellent by impregnating with aqueous dispersions of interpolymers of N-methylol acrylamide or methacrylamide with at least one fluoroalkyl ester of formula Q-OCH2(CF2-CF2)mH where m is 1 t 6, or Q-OCH2(CF2)nF or Q-OCH2CH2(CF2)nF where n is 2 to 12 and Q is acrylyl or methacrylyl, said N-methylol compound constituting 0,25 to 5 weight per cent of the interpolymer, drying the fabric and heating, preferably at 100 DEG  to 150 DEG C.  The treated fabrics may be washed and dry cleaned, but after washing should be ironed to restore maximum repellent effect.  Examples describe the treating of fabrics of (2) cotton and wool, (3 to 9) cotton, (10, 12 and 13) cotton poplin and (11) cotton, wool gabardine, wool worsted, nylon and polyester with aqueous dispersions of interpolymers of N-methylol acrylamide or methacrylamide with (2) 1H,1Hpentadecafluorooctyl acrylate, (3) 1H,1H-nonadecafluorodecyl acrylate, (4, 6 and 8) 1H,1H,11Heicosafluorobendecyl and 1H,1H,7H-dodecafluoroheptyl acrylates, (5 and 9) 1H,1H,11Heicosafluorobendecyl and 1H,1H,5H-octafluoropentyl acrylates or methacrylates, (7) 1H,1H,9Hhexadecafluorononyl acrylate or methacrylate, (10) 1H,1H-pentafluoropropyl acrylate or methacrylate, (11) 1H,1H,9H-hexadecafluorononyl and 1H,1H-pentafluoropropyl acrylates and (12) 1H,1H,2H,2H-tridecafluorooctyl methacrylate; and interpolymers of N-methylol acrylamide with a mixture of methacrylates of formula F(CF2)nCH2CH2O.CO.C(CH3)=CH2 where n is 6, 8 and 10.  Specifications 703,434 and 703,435 are referred to.