Patent GB-904262-A (GB)
Title: Improved polymers
IPC: C08F291/00
Filed: 1960-08-10
Abstract: Repellency to oil and water and resistance to soiling are imparted to surfaces by applying thereto segmented polymers comprising 0,5 to 80% by weight of at least one A segment comprising at least four fluorine-containing monomeric units having a Cn2n+1 group where n is at least 4, the segment containing from 30 to 75% by weight of fluorine derived from said group; and 20 to 99,5% by weight of at least one B segment which comprises at least 5 consecutive monomeric units of an ethylenically unsaturated monomer different from the fluorine-containing monomeric units, this segment containing less than 10% by weight of fluorine from CnF2n+1 groups where n is at least 4 (see Group IV(a)).  Illustrative of such segmented polymers are those made from methyl vinyl ketone, butadiene, chloroprene or natural rubber and acrylic and methacrylic acid esters of N-alkanol perfluoroalkane sulphonamides and omega-perfluoroalkyl alkanols.  The surface to be treated may be of glass, wood, metal, e.g. aluminium, ceramic, plastic, plaster, brick, concrete, asbestos or masonry.  The segmented polymers may be applied to the surfaces either in the form of an organic solution or as an aqueous latex.  The segmented polymer may be used as the sole component in the treating vehicle, or may be used in admixture with other coating media, e.g. latex paints based on polyvinyl acetate, butadienestyrene copolymers or acrylic resins. The examples describe the application of coatings to: (1) aluminium panels, (11) aluminium panels, and (12) microballoons, plywood and aluminium panels. Specifications 857,689 and 904,261 are referred to.ALSO:Graft and block polymers are made which comprise 0,5-80% by weight of at least one A segment comprising at least four fluorinecontaining monomeric units having a CnF2n+1 group where n is at least 4, the segment containing from 30 to 75% by weight of fluorine derived from said group; and 20 to 99,5% by weight of at least one B segment which comprises at least five consecutive monomeric units of an ethylenically unsaturated monomer different from the fluorine containing monomeric units, this segment containing less than 10% by weight of fluorine from CnF2n+1 groups where n is at least 4.  Fluorine containing monomers specified are the acrylic, methacrylic and chloroacrylic esters of N-alkanol perfluoroalkane sulphonamides, 1,1-dihydroperfluoroalkanols, omega-perfluoroalkyl alkanols and 1,1,3-trihydroperfluoroalkanols, 1,1-dihydroperfluoroalkyl acrylamides and vinyl ethers, vinyl and allyl perfluoroalkyl ketones, 1-perfluoroalkenes, 2-perfluoroalkyl ethylenes, 1,1-dihydroperfluoroalkene-1 perfluoroalkyl substituted styrenes and vinyl and allyl esters of perfluoroalkanoic acids. Preferred amongst such monomers are those having the formul <FORM:0904262/IV(a)/1> Ethylenically unsaturated monomers specified are vinyl and vinylidene chlorides and fluorides, vinyl acetate and chloroacetate, acrylonitrile, methacrylonitrile, acrylic, methacrylic and chloroacrylic acids and alkyl esters thereof, acrylamide, methacrylamide, vinyl pyridine, pyrrolidone and carbazole, butadiene, chloroprene, fluoroprene, isoprene, vinyl alkyl ethers, vinyl alkyl ketones, vinylidene cyanide, styrene and alkylated, halogenated and sulphonated styrenes.  The segmented polymers may be prepared by the formation of either A or B segments by the formation of either A or B segments as a prepolymer which either participates by initiation or chain transfer mechanisms in the subsequent reaction in which the dissimilar segments are formed.  The prepolymer may contain groups, e.g. thiol, disulphide, chloro, bromo, iodo, peroxide or hydroperoxide groups or activated hydrogen atoms, which participate in initiation or chain transfer reactions. Prepolymers specified are polyvinyl methyl ketone, polybutadiene, a copolymer of butadiene and monomer II, and natural rubber. Alternatively, segmented polymers may be prepared by the simultaneous polymerization of monomers having widely different reactivity ratios, e.g. chloroprene and one of monomers I-V. Polymerization may be carried out in solution, e.g. in dioxane, or in an aqueous medium which may contain an emulsifier, acetone and mercaptans.  Polymerization initiators specified are ultra-violet light, potassium persulphate and, when using a hydroperoxidized natural rubber latex as a prepolymer, a mixture of ferrous sulphate and triethylenetetramine.  The products, either as aqueous latices or organic solutions, may be used in the treatment of textiles and papers, and in coating compositions to be applied to metallic and nonmetallic surfaces.  In the treatment of textiles the segmented polymers may be used in combination with aminoplasts, sizes, softeners and water repellents.  In the treatment of surfaces the segmented polymers may be added to latex paints based on polyvinyl acetate, a styrenebutadiene copolymer or an acrylic resin. The Specification describes also the preparation of unsegmented copolymers of monomer II with methyl vinyl ketone and butadiene, in the former case the reaction being carried out in solution and in the latter case in aqueous emulsion.  Specifications 857,689 and 904,261 are referred to.ALSO:Resistance to soiling is imparted to fabrics by applying thereto segmented polymers which comprise 0.5 to 80% by weight of at least one A segment comprising at least one   segment comprising at least four fluorine-containing monomeric units having a CnF2n + 1 group, where n is at least 4, the segment containing from 3 to 75% by weight of fluorine derived from said group; and 20 to 99.5% by weight of at least one B segment which comprises at least 5 consecutive monomeric units of an ethylenically unsaturated monomer different from the fluorine-containing monomeric units, this segment containing less than 10% by weight of fluorine from CnF2n + 1 groups, where n is at least 4 (see Group IV(a)).  Illustrative of such segmented polymers are those made from butadiene, chloroprene or natural rubber and acrylic and methacrylic acid esters of N-alkanol perfluoroalkane sulphonamides and omega-perfluoroalkyl alkanols. Fabrics specified are those made from cotton, wool, linen, silk, mohair, jute, ramie, sisal and kenaf and synthetic fibres such as rayon, acetate, acrylic, polyester, polyamide, olefin and glass fibres, and mixtures thereof, e.g. wool/polyester blends and a blend of rayon, polyester fibre, acrylic fibre and mohair.  The segmented polymers may be applied to the fabrics either in the form of an organic solution or as an aqueous latex, and may be used in conjunction with other agents such as crease-resisting resins, e.g. aminoplasts, epoxy resins and polyglycol acetals, sizes, e.g. starch, casein, glue, polyvinyl alcohol and cellulose derivatives; softeners, e.g. polyethylene glycols, polyethylene, dimethyl polysiloxanes, amines and amides derived from fatty acids and ethylene oxide condensation products of such amines and amides; and water-repellents, e.g. waxes, aluminium salts of fatty acids, silicone resins, chromium complexes of fatty acids, N-alkyl amidomethyl pyridinium salts and melamineformaldehyde resin condensates with fatty acid amides.  Specifications 857,689 and 904,261 are referred to.