Patent GB-413666-A (GB)
Title: Improvements in coated and impregnated materials and methods of making same
IPC: C14C11/00
Filed: 1932-10-18
Abstract: Porous or fibrous materials are coated or impregnated with compositions containing polymerization products of a halogen-2-butadiene-1 : 3.  The preparation of the polymerization products, as such or in the form of emulsions, is described in Specifications 387,325, [Group IV], and 387,340.  Examples 1, 2, and 5--7 describe the use of compositions comprising (examples 2 and 7) polymerized chloro-2-butadiene-1 : 3, phenyl-b -naphthylamine (as anti-oxidant), and toluene, with the addition of (example 1) zinc laurate and zinc oxide, which act as curing agents for the polymer, or (example 5) asphalt and zinc oxide or (example 6) zinc oxide and di(methylcyclohexyl) adipate, or (example 3) zinc laurate.  Examples 4 and 8 describe the use of an emulsion of polymerized chloro-2-butadiene-1 : 3 containing sodium oleate and phenyl-b -naphthylamine.  The examples numbered as below describe the use of compositions comprising (10) polymerized chloro-2-butadiene-1 : 3, toluene, zinc oxide, and phenyl-b -naphthylamine, with or without Japan wax; (16) polymerized chloro-2-butadiene-1 : 3, zinc oxide, mineral oil, phenyl-b -naphthylamine, and stearic acid, with or without xylene; (18) polymerized chloro-2-butadiene-1 : 3, phenyl-b -naphthylamine, and zinc oxide; (19) the polymer, mineral oil, phenyl-b -naphthylamine, montan wax, stearic acid, thermatomic black, barytes, zinc oxide, and clay; (21) the polymer, mineral oil, phenyl-b -naphthylamine, mineral rubber, stearic acid, thermatomic black, zinc oxide, and clay; (22) the polymer, boneblack, zinc oxide, phenyl-b -naphthylamine, toluene, ethyl acetate, and butyl acetate; the composition may also include cellulose nitrate (example 23) or (example 24) a reaction product of the polymer with a synthetic resin of the glyptal type; (26) the polymer, titanium oxide, clay, zinc oxide, sienna, turkey umber, toluene, ethyl acetate, butyl acetate, and phenyl-b -naphthylamine; (30) the polymer, paraffin, zinc oxide, phenyl-b -naphthylamine, and toluene; (31) the polymer, toluene, zinc oxide, and phenyl-b -naphthylamine; (33) the polymer, carbon black, toluene, xylene, phenyl-b -naphthylamine, and zinc oxide. Other curing agents, which may replace zinc oxide or zinc laurate when used in the examples above, are zinc dust, zinc butyrate, and salts of copper, lead or iron, e.g. ferric chloride.  The phenyl-b -naphthylamine used as antioxidant in the examples may be replaced by aniline, diphenylamine, benzidine hydroquinone, pyrogallol, or any other rubber anti-oxidant, or by a basic compound, which stabilizes the composition by combining with liberated acid; suitable basic compounds are zinc oxide, magnesium oxide, sodium oleate, zinc laurate, and calcium stearate.  The polymerization products used in the examples may be mixed with oils, resins, waxes, softeners, asphalts, and cellulose esters or ethers; resins specified in this connection are ordinary rosin, ester gum, glyptal resins, coumarone resins, phenol-formaldehyde resins (rosin-modified or not), chlorinated diphenyls or naphthalenes, and m-styrene.  As pigments which may be used, mention is made also of lead chromate, lithopone and iron oxide. Benzene, carbon tetrachloride and chlorobenzene, with or without small amounts of aliphatic hydrocarbons and alcohols, are mentioned as alternative solvents.  The emulsions used may contain proteins, water-soluble gums or resins, or sodium silicate. Polymerized bromo-2-butadiene-1 : 3 may be used as described above instead of the polymerized chloro compound.ALSO:Fabrics or threads are coated or impregnated with compositions containing polymerization products of a halogen-2-butadiene-1 : 3. The treatment improves the mechanical properties of the materials, and enhances their resistance to water, oil, and gases.  The preparation of the polymerization products, as such or in the form of emulsions, is described in Specifications 387,325 and 387,340. Examples 10--12 describe the impregnation of woven fabrics, as follows:--(10) teal (a two-ply cotton fabric laminated with a rubber composition) is impregnated by spreading with a composition comprising polymerized chloro-2-butadiene-1 : 3, toluene, zinc oxide, and phenyl-b -naphthylamine, and then dried and heated; Japan wax may be included in the composition; (11) cotton sheeting is passed through an emulsion of polymerized chloro-2-butadiene-1 : 3 containing sodium oleate and phenyl-b -naphthylamine; (12) woollen fabric is treated with the composition used in example 10. Example 14 describes the treatment of wetted cotton cloth with an emulsion as used in example 11, under such conditions that the cloth is both coated and impregnated.  Example 15 describes the treatment of linen thread with the same emulsion.  In example 24 there is used, as a component of a coating composition, a reaction product of the polymer with a synthetic resin of the glyptal type; the resin may be prepared by heating glycerol, phthalic anhydride, linseed oil acids, and Chinawood oil acids at 225 DEG  C. while passing carbon dioxide through the mixture; the reaction product of the resin and the polymer is prepared by heating the resin with unpolymerized chloro-2-butadiene-1 : 3 to 100 DEG  C. in toluene solution.  Curing agents, which may replace zinc oxide when used in the examples above, are zinc laurate, zinc dust, zinc butyrate, and salts of copper, lead or iron, e.g. ferric chloride.  The phenyl-b -naphthylamine used as antioxidant in the examples may be replaced by aniline, diphenylamine, benzidine, hydroquinone, pyrogallol, or any other rubber antioxidant, or by a basic compound, which stabilizes the composition by combining with liberated acid; suitable basic compounds are zinc oxide, magnesium oxide, sodium oleate, zinc laurate, and calcium stearate.  The polymerization products used in the examples may be replaced by polymers produced in the presence of mineral, animal or vegetable drying or non-drying oils, natural or synthetic resins, gums, waxes, asphalts, sulphur, organic sulphur compounds such as butyl mercaptan, p-thiocresol, tetramethylthiuram disulphide, and mercaptothiazoles and polymerizable substances such as isoprene; alternatively, oils, resins, waxes, softeners, asphalts, and cellulose esters or ethers may be incorporated with the polymers; resins specified in this connection are ordinary rosin, ester gum, glyptal resins, coumarone resins, formaldehyde resins (rosin-modified or not), chlorinated diphenyls or naphthalenes, and m-styrene. Benzene, carbon tetrachloride and chlorobenzene, with or without small amounts of aliphatic hydrocarbons and alcohols, are mentioned as alternative solvents.  The emulsions used may contain proteins, water-soluble gums or resins, or sodium silicate.  Materials treated as described above may be further coated with casein, resin, or pyroxylin finishes.  Polymerized bromo-2-butadiene-1 : 3 may be used as described above instead of the polymerized chloro compound.