Patent GB-389122-A (GB)
Title: Improvements in and relating to the manufacture of halogenated unsaturated non-benzenoid acetylene polymers or their reduction products
IPC: C07C17/02
Filed: 1931-06-04
Abstract: Products ranging from liquids to brittle solids are obtained by halogenating (a) the nonbenzenoid acetylene polymers, particularly mono- and di-vinylacetylene and the acetylene tetramer C8H8, obtainable as described in Specification 384,654, or (b) the incompletely polymerized polymerization products of the said polymers, obtainable as described in Specification 384,655, or (c) the still unsaturated mixed reduction products of the polymers specified under (a) and (b), obtainable as described in Specification 389,108.  Halogenation may be effected with elementary halogen or with an inorganic sulphur-containing halogen compound.  In examples of the use of elementary halogen, (1) divinylacetylene is chlorinated at 20 DEG  C. in carbon tetrachloride or 1 : 1 : 2 : 2-tetrachlorethane to give a product consisting mainly of 1 : 2 : 3 : 4 : 5 : 6-hexachlorohexene-3; (2) a mixture of polymers as under (a) above is simultaneously chlorinated and polymerized by treatment as in example (1) but at 80 DEG  C., giving a viscous oil; iodine may be present as a catalyst (example 3), and example (1) may be modified by omitting the solvent (example 4) and by adding iodine as a catalyst (example 5); (6) a product as under (b) above is treated as in example (1), giving a non-volatile oil or (example 7) a semi-solid mass; bromine or iodine may replace chlorine in any of the examples above, and the iodine used as catalyst may be replaced by iron, mercury, sulphur, mercuric oxide, bromine, ferrous or ferric chloride, or aluminium chloride; the products are useful as drying oils for paints or as adhesives or moulding compositions or linings for chemical apparatus.  Treatment of the materials under (a) and (b) above with sulphuryl or thionyl halides may yield halogenated products free from sulphur or complex esters containing sulphur.  In examples of the use of sulphuryl chloride, (8) divinylacetylene and sulphuryl chloride are reacted at 30-35 DEG  C. to give an oily product, believed to be 3 : 4-dichloro-1 : 3 : 5-hexatriene; the product loses chlorine when heated with sodium acetate or ethylate, sodamide, aqueous caustic alkali, or amines such as butylamines, aniline, or p-toluidine, the products thus obtained frequently being polymerized; (9) a mixture of polymers as under (a) above is treated as in example 8, yielding a mixture of chlorine derivatives; (10) a liquid product as under (b) above is treated as in example 8, yielding a nonvolatile chlorinated oil, the solution of which in toluene, xylene or solvent naphtha is useful as a coating composition; a solvent may be present during the reaction, e.g. carbon p  tetrachloride or 1 : 1 : 2 : 2-tetrachlorethane (example 11); (12) a mixture of polymers as under (a) above is added to boiling sulphuryl chloride, giving a product like that of example 10, or (example 13) is treated in carbon tetrachloride with sulphuryl chloride at a low temperature in the presence of aluminium chloride, giving a semi-liquid chlorinated product; (14) gaseous monovinylacetylene is passed into sulphuryl chloride at 20-40 DEG C., giving a volatile oil, believed to be 1 : 2-dichlorobutadiene-1 : 3 and (or) 1 : 2-dichlorobutine-3, and a non-volatile residue; the products of examples 8-14 have generally the same uses as those of examples 1-7.  Reference is made to the reaction of the acetylene polymers with sulphuryl chloride in the gaseous phase, to the use of ferric and zinc chlorides as catalysts for the reaction and of chloroform, benzoyl chloride, acetyl chloride, liquid sulphur dioxide, and acetic acid as solvents for the reaction mixture, and to the reaction of the acetylene polymers &c. with double thionyl halides such as thionyl chlorbromide.  Treatment of the materials under (a) to (c) above with sulphur halides yields vulcanized halogenated products.  In examples, (15) divinylacetylene is treated with sulphur chloride at a temperature rising to 100 DEG  C., giving a tarry product solidifying in the cold; carbon tetrachloride may be present as a solvent (example 16); (17) an excess of a product as under (b) above is treated with sulphur chloride in toluene, giving a product useful as a coating composition; (18) a product as under (b) above is dissolved in benzene or solvent naphtha and treated with a little sulphur chloride, giving a solution from which a thermoplastic product is obtained by evaporation.  The solid products obtainable as in examples 15-18 are useful in the manufacture of moulding compositions and adhesives; thus, a moulding composition may comprise wood flour and a little phenyl-a -naphthylamine, in addition to one of the said solid products, and may be moulded at 160 DEG  C. under 2000 lb. pressure; an adhesive may comprise a mixture of one of the said products with silica, clay, asbestine, or wood flour, with or without a solvent.  Products useful as coating compositions are obtained by treating polymerization products as under (b) above with sulphur chloride under various conditions.  In examples, (19) a product as under (b) above is treated in toluene with sulphur chloride; (20) a composition prepared as in example (19) is mixed with a product as under (b) above and toluene; (21) as in example 19, but using different proportions; (22) as in example 19, but using benzene or solvent naphtha as the solvent.  The compositions may contain softeners, resins, driers, and fillers, e.g. silica, graphite or barytes. Examples of the use of the coating compositions are given as follows: (23) pickled steel or an iron pot or a cement floor is coated with the product of example 20 and then with a product as under (b) above; (24) a product as under (b) above is mixed with a filler and treated in solvent naphtha with sulphur chloride; the product is applied to an iron pot, which is afterwards coated with a product as under (b) above; the coating, when set, is steamed and finally treated with a solution of bromine in carbon tetrachloride; (25) a product prepared as in example 15 is used as a coating composition, alone or with fillers and volatile solvents; the coatings harden in the air, or hardening may be accelerated by steaming or baking or by treatment with oxygen, bromine, or chlorine; copper, nickel and wood are mentioned as other materials which may be coated.  In examples of the halogenation of products as under (c) above, (26) a reduction product is chlorinated at 20-30 DEG  C. in carbon tetrachloride to give a viscous oil comprising chlorohexanes, particularly 1 : 2 : 5 : 6-tetrachlorohexane; (27) a reduction product is brominated at below 10 DEG  C. in carbon tetrachloride, giving a mixture of bromohexanes.ALSO:Products useful in the manufacture of coating compositions are obtained by halogenating (a) the non-benzenoid acetylene polymers, particularly mono- and di-vinylacetylene and the acetylene tetramer C8H8, obtainable as described in Specification 384,654 or (b) the incompletely polymerized polymerization products of the said polymers, obtainable as described in Specification 384,655, or (c) the still unsaturated mixed reduction products of the polymers specified under (a) and (b), obtainable as described in Specification 389,108.  In examples of the production of coating compositions, (10) a liquid product as under (b) above is treated with sulphuryl chloride, yielding a non-volatile chlorinated oil, the solution of which in toluene, xylene or solvent naphtha is useful as a coating composition; (12) a mixture of polymers as under (a) above is added to boiling sulphuryl chloride, giving a product like that of example 10; (19) a product as under (b) above is treated in toluene with sulphur chloride to produce a coating composition; (20) a composition prepared as in example 19 is mixed with a product as under (b) above and toluene; (21) as in example (19), but using different proportions; (22) as in example (19), but using benzene or solvent naphtha as the solvent.  The compositions may contain softeners, resins, driers, and fillers, e.g. silica, graphite or barytes.  Examples of the use of the coating compositions are given as follows:--(23) pickled steel or an iron pot or a cement floor is coated with the product of example 20 and then with a product as under (b) above; (24) a product as under (b) above is mixed with a filler and treated in solvent naphtha with sulphur chloride; the product is applied to an iron pot, which is afterwards coated with a product as under (b) above; the coating, when set, is steamed and finally treated with a solution of bromine in carbon tetrachloride; (25) a product prepared from divinylacetylene and sulphur chloride at 100 DEG  C., is used as a coating composition, alone or with fillers and volatile solvents; the coatings harden in the air, or hardening may be accelerated by steaming or baking or by treatment with oxygen, bromine, or chlorine; copper, nickel and wood are mentioned as other materials which may be coated.ALSO:Products useful in the manufacture of moulding-compositions or adhesives are obtained by halogenating (a) the non-benzenoid acetylene polymers, particularly mono- and di-vinylacetylene and the acetylene tetramer C8H8, obtainable as described in Specification 384,654, [Group IV], or (b) the incompletely polymerized polymerization products of the said polymers, obtainable as described in Specification 384,655, or (c) the still unsaturated mixed reduction products of the polymers specified under (a) and (b), obtainable as described in Specification 389,108.  Halogenation may be effected with elementary halogen or with an inorganic sulphur-containing halogen compound.  In examples of the use of elementary halogen, (1) divinylacetylene is chlorinated at 20 DEG  C. in carbon tetrachloride or 1 : 1 : 2 : 2-tetrachlorethane to give a product consisting mainly of 1 : 2 : 3 : 4 : 5 : 6-hexachlorohexene-3; (2) a mixture of polymers as under (a) above is simultaneou