| 摘要 |
Products including volatile or viscous liquids, rubber substitutes, and hard solids are prepared by polymerizing halogen-2-butadienes-1 : 3, which are obtainable as described in Specification 387,325. The halogenbutadienes polymerize slowly when allowed to stand in the absence of light and air, but polymerization may be accelerated by the application of heat and pressure, by the action of natural or artificial light, and by the presence of oxygen or air or a catalyst, e.g. benzoyl peroxide, oxidized turpentine, sodium peroxide, lead peroxide, or hydrogen peroxide. Examples 1-21 describe the polymerization of chloro-2-butadiene-1 : 3 under various conditions as indicated above. The polymerization may be retarded or controlled by addition of any of the following substances, called inhibitors: pyrogallol; catechol; guaiacol; hydroquinone; p-hydroxydiphenyl; phenol; benzoquinone; a-naphthoquinone; tetraphenylhydrazine; m-toluylenediamine; thiodiphenylamine; phenyl-a - or -b-naphthylamine; diphenylguanidine; diphenylamine; dibenzylamine; aniline; piperidine; pyridine; dimethylaniline; quinoline; ethylenediamine; di - or tri - butylamine; triethylamine; heptylamine; benzidine; nitro- or trinitro-benzene; p butyl- or benzylmercaptan; thioacetic acid; thiobenzanilide; thiophenol; thiocresol; methyl or ethyl sulphide; n-propyl or allyl sulphide; n-butyl or n-heptyl sulphide; benzyl or diphenyl sulphide; methyl, n-propyl, or n-butyl disulphide; ethyl thioacetate; diethyl dithiooxalate; ethyl ethylxanthate; thioacetamide; thio-b-naphthol; ethyl selenide; iodine; or bromine. Examples 22-34 describe the polymerization of chloro-2-butadiene-1 : 3 in the presence of an inhibitor. The polymerization may be further controlled by addition of a solvent or solute, which may be (1) a volatile solvent capable of dissolving the halogenbutadiene and its polymer, e.g. benzene, toluene, xylene, cymene; diethyl ether, chloroform, carbon tetrachloride; turpentine, ethylene chloride, pyridine, or carbon bisulphide; (2) a non-volatile compound soluble in or capable of dissolving the halogenbutadiene and its polymer, e.g. spindle oil, machine oil, refined mineral oil, petroleum jelly, diphenyl ether, ethyl benzoate, camphor, cottonseed oil, linseed oil, corn oil, cocoanut oil, soya bean oil, cod-liver oil, tricresyl phosphate, shellac, or stearic acid; (3) a polymerizable liquid capable of dissolving the halogenbutadiene, e.g. isoprene, styrene, China-wood oil, indene, vinylacetylene, divinylacetylene, or vinyl acetate; (4) a liquid which is a solvent for the halogenbutadiene but not for its polymer, e.g. ethyl alcohol or petroleum ether. Examples 35-41 describe the polymerization of chloro-2-butadiene-1 : 3 in the presence of a solvent as under (1) above, giving solutions which may be used as cements or coating or impregnating compositions, or may be evaporated to yield rubber-like products. Examples 42-50 describe the polymerization of chloro-2-butadiene-1 : 3 in the presence of a solvent or solute as under (2) above, the solvent or solute remaining in the product and acting as a softener, plasticizer, or lubricant. Examples 51, 53 describe the polymerization of chloro-2-butadiene-1 : 3 in the presence of a polymerizable solvent, giving mixed polymerization products in the form of elastic masses. Examples 54 and 55 describe the polymerization of chloro-2-butadiene-1 : 3 in the presence of a solvent as under (4) above, with the production of precipitated plastic products. Examples 56 and 57 describe coating compositions comprising solutions prepared as in examples 35-41 and containing (example 56) titanox and a little phenyl-b-naphthylamine or (example 57) carbon black and a little phenyl-b-naphthylamine, which may be replaced by any other of the usual rubber-antioxidants; reference is made also to the use of the following pigments and fillers: lithopone, zinc oxide, white lead, chrome orange, iron oxide, Prussian blue, red lakes, whiting, asbestine and silica; the compositions may contain also an acid-acceptor, e.g. sodium oleate. Examples 58-65 describe the polymerization of chloro-2-butadiene-1 : 3 under conditions adapted to yeild a partial polymerization product which is soluble in the usual rubber solvents, resembles unvulcanized rubber in physical properties, and can be shaped and then further polymerized by heat and (or) pressure to give a product resembling vulcanized rubber; the partial polymerization product is separated from unpolymerized material and volatile polymerization products by distillation, preferably under reduced pressure, or by treating the reaction product with a liquid which dissolves the unpolymerized material but not the desired rubber-like product; methyl, ethyl, propyl, isopropyl or butyl alcohol, acetone, methylethyl ketone, and diethyl ketone are suitable liquids for this purpose. The product of examples 58-65 may be mixed, during or after its production, with fillers, anti-oxidants, and other usual ingredients of rubber compositions; addition of a vulcanizing agent such as sulphur or selenium before further polymerization is unnecessary. Examples 66-73 describe the further treatment of the product of examples 58-65 as follows: (66) a mixture of the product with a little oleic acid and phenyl-b-naphthylamine is calendered on broadcloth, which is then heated to 130 DEG C.; (67) a mixture of the product with zinc oxide and a little phenyl-b-naphthylamine is moulded under pressure into a sheet and heated in the mould to 140 DEG C.; (68) a mixture of the product with zinc oxide and a little stearic acid and catechol is mixed with benzene to form a cement, from which a balloon is made by repeatedly dipping a suitable form into the cement, drying at a temperature below 50 DEG C. between successive dippings, and finally heating at 130 DEG C.; (69) a mixture of the product with zinc oxide and clay and subordinate amounts of mineral oil, paraffin, pine-tar, and phenyl-b-naphthylamine is formed into insulation for copper wire, which is then embedded in soapstone and heated in steam to 135 DEG C.; (70) a mixture of the product with zinc oxide and clay and subordinate amounts of stearic acid, red oxide, and hydroquinone is mixed with benzene to form a dough, which is spread on broadcloth, dried, and heated to 135 DEG C.; (71) a mixture of the product with thermatomic carbon, zinc oxide, and subordinate amounts of lithopone, stearic acid, and phenyl-b-naphthylamine is moulded to form a gasket, and heated in the mould to 138 DEG C.; (72) a mixture of the product with small amounts of oleic acid, phenyl-b-naphthylamine and zinc dust is calendered on cotton cloth and heated to 70 DEG C.; (73) for the manufacture of a hosepipe, two compositions are prepared, viz.: (1) a mixture of the product with zinc oxide and thermatomic carbon and subordinate amounts of stearic acid and phenyl-b-naphthylamine, and (2) a mixture of smoked sheets with zinc oxide and subordinate amounts of sulphur, stearic acid, mercaptobenzothiazole, and blue pigment; a mandrel is covered with a sheet of the first mixture, on which two layers of fabric coated with the second mixture are superimposed, followed by a sheet of the second mixture; the whole is wrapped in moist cloth and vulcanized in steam at 40 lb. pressure. The following substances are also specified as suitable for inclusion in compositions containing the product of examples 58-65: blanc fixe, whiting, lime, magnesium carbonate, magnesia, slate flour, mineral rubber, vulcanized oil, resin, diphenylguanidine, sulphur, cork dust, ground leather, cotton, sawdust and asbestos. Example 74 describes the polymerization of bromo-2-butadiene-1 : 3 under conditions similar to those of examples 1-21 above; the polymerization products of bromo - 2 - butadiene - : 3 resemble those of the chloro compound, and can be used or further treated as described above in connection with the chloro compound. ALSO: Products useful as constituents of coating-compositions are prepared by polymerising halogen 2-butadienes 1- : 3, which are obtainable as described in Specification 387,325, [Group IV]. The halogenbutadienes polymerize slowly when allowed to stand in the absence of light and air, but polymerization may be accelerated by the application of heat and pressure, by the action of natural or artificial light, and by the presence of oxygen or air or a catalyst, e.g. benzoyl peroxide, oxidized turpentine, sodium peroxide, lead peroxide, or hydrogen-peroxide. Examples 1-21 describe the polymerization of chloro-2-butadiene-1 : 3 under various conditions as indicated above. The polymerization may be retarded or controlled by addition of any of the following substances, called inhibitors : pyrogallol; catechol; guaiacol; hydroquinone; p-hydroxydiphenyl; phenol; benzoquinone; a-naphthoquinone; tetraphenylhydrazine; m-toluylenediamine; thiodiphenylamine; phenyl a- or b-naphthylamine; diphenylguanidine; diphenylamine; dibenzylamine; aniline; piperidine; pyridine; dimethylaniline; quinoline; ethylenediamine; di- or tri-butylamine; triethylamine; heptylamine; benzidine; nitro- or trinitro-benzene; butyl- or benzyl-mercaptan; thioacetic acid; thiobenzanilide; thiophenol; thiocresol; methyl or ethyl sulphide; n-propyl or allyl sulphide; n-butyl or n-heptyl sulphide; benzyl or diphenyl sulphide; methyl n-propyl or n-butyl disulphide; ethyl thioacetate; diethyl dithiooxalate; ethyl ethylxanthate; thioacetamide; thio-b-naphthol; ethyl selenide; iodine, or bromine. Examples 22-34 describe the polymerization of chloro-2-butadiene-1 : 3 in the presence of an inhibitor. The polymerization may also be effected in the presence of a volatile solvent capable of dissolving the halogenbutadiene and its polymer, e.g. benzene, toluene, xylene, cymene; diethyl ether, chloroform, carbon tetrachloride; turpentine, ethylene chloride, pyridine, or carbon bisulphide. Examples 35-41
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