Patent GB-468658-A (GB)
Title: Improvements in vulcanisation of rubber
IPC: C08K5/00
Filed: 1936-08-11
Abstract: The vulcanization of rubber is accelerated by the addition to the mix of a disubstituted carbamyl-1-thiazyl sulphide in conjunction with a basic nitrogen containing organic accelerator. The former materials are prepared by the reaction of a mercaptothiazole, preferably in the form of its alkali salt with a disubstituted carbamyl halide.  The compounds fall within the general formula <FORM:0468658/IV/1> where T is a 1-thiazyl radical and R and R1 are the residues of a secondary amine.  These may be aliphatic, aralkyl, alicyclic, heterocyclic, or aromatic radicals, of which the following are specified: Methyl, ethyl, butyl, phenyl, cyclohexyl, benzyl, beta-phenethyl, alpha-furfuryl, and tetrahydro-alpha-furfuryl.  R and R1 may also be joined together to form a poly-methylene radical which may be interrupted by oxygen or sulphur.  The compounds are prepared by bringing the mercaptothiazole salt and the carbamyl halide (preferably the chloride) together in a solvent and heating.  A long list of suitable mercaptothiazoles and disubstituted carbamyl halides is given, of which the following are typical, the 1-mercaptonaphthothiazoles, 1-mercapto-4-nitro-benzothiazole, 1-mercapto-4-chlor-benzothiazole, 1-mercapto-4-nitro-5-chlor-benzothiazole, 1-mercapto-3-phenyl-benzothiazole, 1-mercapto-3-methoxy-benzothiazole, 1-mercapto-5-hydroxy-benzothiazole, and other halogen, nitro, hydroxy, alkoxy and amino substituted arylene thiazoles, together with diethyl carbamine chloride, dicyclohexyl carbamine chloride, di-(o- or p-tolyl) carbamine chloride, N-ethyl cyclohexyl carbamine chloride, di-(tetrahydro-alpha-furfuryl) carbamine chloride, pentamethylene carbamine chloride, di-(o- or p-phenetidyl) carbamine chloride, and di-(alpha or beta-naphthyl) carbamine chloride.  In an example, a suspension of sodium benzothiazyl mercaptide in a solution of diphenyl carbamine chloride in benzene is refluxed for 1 hour, cooled, and the resulting diphenyl carbamyl-1-benzothiazyl sulphide filtered and washed.  This is used in conjunction with diphenylguanidine, and tests are given to show its efficiency in a rubber mix.  Organic basic nitrogen containing accelerators which may be used with the above disubstituted carbamyl-1-thiazyl sulphides are di-o-tolyl guanidine, 2-4-diamino-diphenylamine, p-p1-diamino-diphenyl-methane, diphenylguanidine neutral phthalate, and butyl ammonium oleate.  Specification 360,949 is referred to.ALSO:The vulcanization of rubber is accelerated by the addition to the mix of a disubstituted carbamyl -1-thiazyl sulphide in conjunction with a basic nitrogen-containing organic accelerator. The former materials are prepared by the reaction of a mercapto-thiazole, preferably in the form of its alkali salt with a disubstituted carbamyl halide.  The compounds fall within the general formula T-S- <FORM:0468658/V/1> where T is a 1-thiazyl radical, and R and R1 are the residues of a secondary amine.  These may be aliphatic, aralkyl, alicyclic, heterocyclic or aromatic radicals of which the following are specified: methyl, ethyl, butyl, phenyl, cyclohexyl, benzyl, betaphenethyl, alpha furfuryl, and tetrahydro alpha furfuryl.  R and R1 may also be joined together to form a polymethylene radical which may be interrupted by oxygen or sulphur.  A long list of suitable mercaptothiazoles and carbamyl halides is given.  In an example a suspension of sodium benzothiazyl mercaptide in a solution of diphenyl carbamine chloride in benzene is refluxed or one hour, cooled, and the resulting diphenyl carbamyl-1-benzothiazyl sulphide filtered and washed.  This is used in conjunction with diphenylguanidine, and tests are given to show its efficiency in a rubber mix.  Organic basic nitrogen-containing accelerators which may be used in conjunction with the above disubstituted carbamyl-1-thiazyl sulphides are di-o-tolyl guanidine, 2-4-diamino diphenyl-amine, p-p1-diamino-diphenylmethane, diphenylguanidine neutral phthalate, and butyl ammonium oleate.  Specification 360,949 is referred to.