Patent GB-496560-A (GB)
Title: Improvements in treatment of rubber
IPC: C08K5/00
Filed: 1937-05-31
Abstract: The vulcanization of rubber is accelerated by the addition to the mix of an azine sulphide accelerator of the general formula T-Sn-Y, where T represents the azine nucleus, Y represents hydrogen, T, or a salt or esterforming element or group, and n is one or a multiple of one. The azine nucleus embodies four carbon atoms, one nitrogen atom, and a member of the oxygen family of the periodic table having an atomic weight of not more than 32; one of the carbon atoms of the azine ring being directly intermediate the two hetero atoms and directly linked to a non-nuclear mercapto sulphur atom.  The essential group of the compounds of the invention is <FORM:0496560/IV/1> where X represents sulphur or oxygen.  The hydrogen of the mercapto group is replaceable by metal, or other salt-forming group or an azine monosulphide or polysulphide.  The saltforming group may be a metal or an amine, including the ammonium or alkyl aryl or aralkyl substituted ammonium group, and the ester forming groups may be acyclic, carbo-cyclic or heterocyclic groups. Examples are alkali and alkaline earth metals such as sodium or calcium, heavy metals such as lead, zinc, or cadmium and alkyl, aryl, &c. radicals.  The groups attached to the azine nucleus may be saturated or unsaturated, substituted or unsubstituted.  In examples: (1) o-amino benzyl alcohol, carbon disulphide, potassium hydroxide, and ethyl alcohol are refluxed on the steam bath to give 3-mercapto-benzo-2-4-1-thiazine; (2) carbon disulphide is added to a caustic soda solution of gamma brom propylamine hydrobromide to give 2 - mercapto - dihydro - metathiazine; (3) o-amino phenyl-dimethyl carbinol, carbon disulphide and potassium hydroxide are refluxed to give 3-mercapto-1-dimethyl benzo-2-4-1-oxazine; (4) anthranilic acid, carbon disulphide and potassium hydroxide are refluxed to give 3-mercapto-1-oxy-benzo-2-4-1 thiazine; (5) peri-amino naphthol, carbon disulphide, potassium hydroxide and ethyl alcohol are refluxed to give 2-mercapto-peri-naphtho-meta oxazine; (6) an alkaline alcoholic solution of 3-mercapto-1-dimethyl benzo 2-4-1-oxazine is reacted with an alcoholic solution of 2-4-dinitrochlor-benzene to give 2-4-dinitro-phenyl-1-dimethyl-benzo-2-4-1-oxazine-3-sulphide; (7) a solution of chlorine in caustic soda is slowly added to 3-mercapto-1-dimethyl benzo-2-4-1 oxazine to give bis (1-dimethyl benzo-2-4-1-oxazine)-3 disulphide; (8) a caustic soda solution of 3-mercapto-1-dimethyl-benzo 2-4-1-oxazine is slowly mixed with an aqueous solution of zinc sulphate to give a precipitate of the corresponding zinc salt; (9) 3-mercapto-1-dimethyl benzo-2-4-1 oxazine is converted into its amine salt by treatment in aqueous solution with a commercial mixture of methyl-, and ethyl amines. The salts being water-soluble are useful for incorporation in latex mixes.ALSO:The vulcanization of rubber is accelerated by the addition to the mix of an azine sulphide accelerator of the general formula T-Sn-Y where T represents the azine nucleus, Y represents hydrogen, T, or a salt or ester forming element or group, and n is one or a multiple of one.  The azine nucleus embodies four carbon atoms, one nitrogen atom, and a member of the oxygen family of the periodic table, having an atomic weight of not more than 32; one of the carbon atoms of the azine nucleus being directly intermediate the two hetero atoms and directly linked to a non-nuclear mercapto sulphur atom. The essential group of the compounds of the invention is <F1> where X represents sulphur or oxygen.  The hydrogen of the mercapto group is replaceable by metal, or other salt forming group or an azine monosulphide or polysulphide.  The salt forming group may be a metal or an amine, including the ammonium or alkyl, aryl, or substituted ammonium group and the salt forming groups may be acyclic, carbocyclic or heterocyclic groups.  Examples are alkali or alkaline earth metals such as sodium or calcium, heavy metals such as lead zinc or cadmium and alkyl aryl &c. radicals.  The groups attached to the azine nucleus may be saturated or unsaturated, substituted or unsubstituted.  In examples: (1) o-amino benzyl alcohol, carbon disulphide, potassium hydroxide and ethyl alcohol are refluxed on the steam bath to give 3-mercapto-benzo-2-4-1 thiazine; (2) carbon disulphide is added to a caustic soda solution of gamma brom propylamine hydrobromide to give 2-mercapto-dihydro-meta-thiazine; (3) -o-amino phenyl dimethyl carbinol, carbon disulphide and potassium hydroxide are refluxed to give 3-mercapto-1-dimethyl-benzo-2-4-1-oxazine; (4) anthranilic acid, carbon disulphide and potassium hydroxide are refluxed to give 3-mercapto-1-oxy benzo-2-4-1-thiazine; (5) peri-amino-naphthol, carbon disulphide, potassium hydroxide and ethyl alcohol are refluxed to give 2-mercaptoperi-naphtho-meta-oxazine; (6) an alkaline solution of 3-mercapto-1-dimethyl benzo-2-4-1-oxazine is reacted with an alcoholic solution of 2-4-dinitro chlor benzene to give 2-4-di-nitro phenyl-1 dimethyl-benzo-2-4-1 oxazine-3-sulphide; (7) a solution of chlorine in caustic soda is slowly added to 3-mercapto-1-dimethyl-benzo-2-4-1 oxazine to give Bis(1-dimethyl-benzo-2-4-1-oxazine)-3 disulphide; (8) a caustic soda solution of 3-mercapto-1-dimethyl benzo 2-4-1 oxazine is slowly mixed with an aqueous solution of zinc sulphate to give a precipitate of the corresponding zinc salt; (9) 3-mercapto-1-dimethyl benzo-2-4-1 oxazine is converted into its amine salt by treatment in aqueous solution with a commercial mixture of methyl-, and ethyl amines.  The salts being water soluble are useful for incorporation in latex mixes.