Patent GB-434806-A (GB)
Title: Improvements in or relating to rubber vulcanisation
IPC: C07D277/80
Filed: 1934-03-01
Abstract: Products suitable for use as accelerators for the vulcanization of rubber are prepared by reacting an isocyclic saturated organic base with a mercaptoarylthiazole or di- or polysulphide thereof, or with thiuram di- or polysulphide or with aryldithiocarboxylic acid disulphides.  Starting materials comprise decahydro-a -and b -naphthylamine, bornylamine, dibornylamine, methylbornylamine, ethylbornylamine, carylamine, cyclohexylamine, dicyclohexylamine, cyclohexylmethylamine, cyclohexylethylamine on the one hand, and mercaptobenzthiazole, mercaptotolylthiazole, mercaptonaphthothiazole, dibenzthiazyl di- and polysulphides, tetramethylthiuram di- and polysulphides, tetraethylthiuramdisulphide, dithiobenzoic acid disulphide and dithiosalicylic acid disulphide.  The products are relatively stable and give no offensive odour to the vulcanized rubber.  In use, these accelerators may be incorporated with other substances modifying the vulcanization of the rubber mix, for example diphenylguanidine.  In examples, reaction of the following products is described and details are furnished showing their effectiveness when employed in vulcanizing rubber mixes: cyclohexylamine and mercaptobenzthiazole (this product may be used in conjunction with di- or triphenylguanidine or di-o-tolylguanidine as an accelerator), dicyclohexylamine and mercaptobenzthiazole, cyclohexylamine, dicyclohexylamine and mercaptobenzthiazole, dibenzthiazyldisulphide and cyclohexylamine, tetramethylthiuram disulphide and cyclohexylamine.  A sample has been furnished under Sect. 2 (5) of a product prepared by reacting dithiobenzoyldisulphide and cyclohexylamine.  Specification 286,749, [Class 2 (iii)], is referred to.  The Specification as open to inspection under Sect. 91 relates to the production of compounds by reacting an isocyclic saturated organic base with a member of a class of organic compounds possessing the grouping <FORM:0434806/IV/1> , wherein R stands for nitrogen, carbon or sulphur, X for sulphur or nitrogen and Y for sulphur or the acidic hydrogen atom of a mercaptothiazole, and to the use of such compounds in the vulcanization of rubber; it is also stated that retarding agents to the vulcanization process may be incorporated in conjunction with the foregoing accelerators, for example, aniline acid phthalate (reacting aniline hydrochloride and sodium acid phthalate in aqueous solution) or diphenylguanidine phthalate, and illustrative details of the use of such retarders in conjunction with the accelerators in rubber mixes are given.  This subject-matter does not appear in the Specification as accepted.ALSO:Rubber is vulcanized by heating in presence of sulphur (or a sulphur bearing material) and an accelerator which comprises the reaction product of an isocyclic saturated organic base and a mercaptoarylthiazole or di- or polysulphide thereof, or with thiuram di- or polysulphide or with aryldithiocarboxylic acid disulphides.  Starting materials for such reaction products are decahydro-a - and b -naphthylamine, bornylamine, dibornylamine, methylbornylamine, ethylbornylamine, carylamine, cyclohexylamine, dicyclohexylamine, cyclohexylmethylamine, cyclohexylethylamine, and these reacted with the above mercapto or sulphide derivatives yield products which are relatively stable and impart no offensive odour to the vulcanized rubber.  In use these products may be incorporated with other substances modifying the vulcanization of the rubber mix for example diphenylguanidine.  In examples reaction of the following products is described and details are furnished showing their effectiveness when employed as accelerators in vulcanizing rubber mixes: cyclohexylamine and mercaptobenzthiazole (this product may be used in conjunction with di- or triphenylguanidine or di-o-tolylguanidine as an accelerator), dicyclohexylamine and mercaptobenzthiazole, cyclohexylamine, dicyclohexylamine and mercaptobenzthiazole, dibenzthiazyldisulphide and cyclohexylamine, tetramethylthiuram disulphide and cyclohexylamine.  A sample has been furnished under Sect. 2 (5) of a product prepared by reacting dithiobenzoyldisulphide and cyclohexylamine.  Specification 286,749, [Class 70], is referred to.  The Specification as open to inspection under Sect. 91 relates to the use of compounds obtained by reacting an isocyclic saturated organic base with a member of a class of organic compounds possessing the grouping <FORM:0434806/V/1> , wherein R stands for nitrogen, carbon or sulphur, X for sulphur or nitrogen and Y for sulphur or the acidic hydrogen atom of a mercaptothiazole, as accelerators in the vulcanizing of rubber. The use of retarding agents in conjunction with these accelerators is also mentioned, for example aniline acid phthalate or diphenyl guanidine phthalate and illustrative details are given of such use.  This subject-matter does not appear in the Specification as accepted.