Patent GB-453921-A (GB)
Title: Process for sulphurising organic compounds having unsaturated linkages of an aliphatic character
IPC: H01H71/52
Filed: 1935-03-21
Abstract: Organic substances having unsaturated linkages of an aliphatic character are sulphurized and, in some cases, also polymerized, by treatment with sulphur at an elevated temperature, preferably over 100 DEG  C., in the presence of hydrogen sulphide under such conditions that the hydrogen sulphide is maintained in contact with the reactants.  Basic or other substances which act as sulphur carriers may be present during the reaction, e.g. ammonia, hydrazine, aliphatic, aromatic or heterocyclic amines, piperidine, acid amides, or vulcanization acceleration such as di- or tri-substituted guanidines, thiuramsulphides, or cyclohexylethylamines, either alone or mixed together, and if desired, in the presence of solid or liquid loading materials or mineral oils.  Ammonium hydrosulphide may be used as a source of hydrogen sulphide.  The process may be applied to the treatment of animal, vegetable or mineral oils to produce factis or materials suitable for use in the manufacture of soaps, impregnating media or paints; to the treatment of unsaturated alcohols and esters of the terpene series, ethereal oils or vinylacetate; for the manufacture of rubber goods from caoutchouc and of vulcanized products from balata or guttapercha.  Rubber may be vulcanized by exposing layers of rubber containing the necessary additions, e.g. sulphur &c. to moderate heat in an atmosphere of hydrogen sulphide.  Partially sulphurized oils may also be obtained, either for use as such or for further treatment, e.g. by sulphur monochloride.  Such products are thick, almost colourless, oils or semi-solids which may be used as liquid or plastic rubber substitute or in paints or impregnating media.  According to examples: (1) castor oil is treated at 150 DEG  C. with sulphur and a catalyst, e.g. tetra-methyl-thiuram-disulphide, hydrogen sulphide being passed through the mass.  When the mass solidifies, it is held at 130 DEG C. until the desired degree of polymerization occurs. It is further treated in the same manner as ordinary brown rubber substitute; (2) cinnamic acid ethyl ester, sulphur and piperidine are mixed.  On introducing hydrogen sulphide, reaction begins at 60 DEG  C.  The known reaction with sulphur alone only takes place above 220 DEG  C. Styrene reacts in a similar manner. Specifications 243,394, [Class 90], and 360,993 are referred to.  The Specification as open to inspection under Sect. 91 describes also treatment with hydrogen polysulphides, particularly for the manufacture of rubber substitute. Stabilizing agents may be added which raise the surface tension, e.g. halogenated hydrocarbons, e.g. tetrachlormethane, methylene bromide, di-chlorethylenes, or di-chlorethane.  This subject-matter does not appear in the Specification as accepted.ALSO:Organic substances having unsaturated linkages of an aliphatic character are sulphurized and, in some cases, also polymerized, by treatment with sulphur at an elevated temperature, preferably over 100 DEG  C., in the presence of hydrogen sulphide under such conditions that the hydrogen sulphide is maintained in contact with the reactants.  Basic or other substances which act as sulphur carriers may be present during the reaction, e.g. ammonia, hydrazine, aliphatic, aromatic or heterocyclic amines, piperidine, acid amides, or vulcanization accelerators such as di- or tri-substituted guanidines, thiuramsulphides, or cyclohexylethylamines, either alone or mixed together, and if desired, in the presence of solid or liquid loading materials or mineral oils.  Ammonium hydrosulphide may be used as a source of hydrogen sulphide.  The process may be applied to the treatment of animal, vegetable, or mineral oils to produce factis or materials suitable for use in the manufacture of soaps, impregnating media or paints; to the treatment of unsaturated alcohols and esters of the terpene series, ethereal oils or vinylacetate; for the manufacture of rubber goods from caoutchouc and of vulcanized products from balata or guttapercha.  Rubber may be vulcanized by exposing layers of rubber containing the necessary additions, e.g. sulphur &c., to moderate heat in an atmosphere of hydrogen sulphide.  Partially sulphurized oils may also be obtained, either for use as such or for further treatment, e.g. by sulphur monochloride.  Such products are thick, almost colourless, oils or semi-solids, which may be used as liquid or plastic rubber substitute or in paints or impregnating media.  According to an example castor oil is treated at 150 DEG  C. with sulphur and a catalyst, e.g. tetra-methylthiuram-disulphide, hydrogen sulphide being passed through the mass.  When the mass solidifies, it is held at 130 DEG  C., until the desired degree of polymerization occurs.  It is further treated in the same manner as ordinary brown rubber substitute.  Specifications 243,394, [Class 91], and 360,993, [Group IV], are referred to.  The Specification as open to inspection under Sect. 91 describes also treatment with hydrogen polysulphides, particularly for the manufacture of rubber substitute.  Stabilizing agents may be added which raise the surface tension, e.g. halogenated hydrocarbons, e.g. tetrachlorethane, methylene bromide, dichlorethylenes, or di-chlorethane.  This subject-matter does not appear in the Specification as accepted.ALSO:Organic substances having unsaturated linkages of an aliphatic character are sulphurized and, in some cases, also polymerized, by treatment with sulphur at an elevated temperature, preferably over 100 DEG  C., in the presence of hydrogen sulphide under such conditions that the hydrogen sulphide is maintained in contact with the reactants.  Basic or other substances which act as sulphur carriers may be present during the reaction, e.g. ammonia, hydrazine, aliphatic, aromatic or heterocyclic amines, piperidine, acid amides, or vulcanization accelerators such as di- or tri-substituted guanidines, thiuramsulphides, or cyclohexyhethylamines, either alone or mixed together, and if desired, in the presence of solid or liquid loading materials or mineral oils.  Ammonium hydrosulphide may be used as a source of hydrogen sulphide.  The process may be applied for the manufacture of rubber goods from caoutchouc and of vulcanized products from balata or guttapercha.  Rubber may be vulcanized by exposing layers of rubber containing the necessary additions, e.g. sulphur &c., to moderate heat in an atmosphere of hydrogen sulphide. Partially sulphurized oils may also be obtained, either for use as such or for further treatment, e.g. by sulphur monochloride.  Such products are thick, almost colourless, oils or semi-solids, which may be used as liquid or plastic rubber substitute.  According to examples: (1) castor oil is treated at 150 DEG  C. with sulphur and a catalyst, e.g. tetra - methyl - thiuram - disulphide, hydrogen sulphide being passed through the mass.  When the mass solidifies, it is held at 130 DEG  C. until the desired degree of polymerization occurs.  It is further treated in the same manner as ordinary brown rubber substitute; (2) cinnamic acid ethyl ester, sulphur and piperidine are mixed.  On introducing hydrogen sulphide, reaction begins at 60 DEG C.  The known reaction with sulphur alone only takes place above 220 DEG  C.  Styrene reacts in a similar manner.  Specifications 243,394, [Class 70], and 360,993, [Group IV], are referred to.  The Specification as open to inspection under Sect. 91 describes also treatment with hydrogen polysulphides, particularly for the manufacture of rubber substitute.  Stabilizing agents may be added which raise the surface tension, e.g. halogenated hydrocarbons, e.g. tetrachlorethane, methylene bromide, di-chlorethylenes, or di-chlorethane.  This subject-matter does not appear in the Specification as accepted.