Patent GB-475220-A (GB)
Title: Improvements in vulcanization of rubber
IPC: C08K5/00
Filed: 1936-11-13
Abstract: The vulcanization of rubber is accelerated by the addition to the mix of a compound of the general formula T--S--CH2--O--R where T represents a 1-thiazyl radical and R represents either an acyl group or an aromatic carbamyl radical.  In the case where R is an acyl radical the compounds are preferably made by reacting a thiazyl 1-thio methylene hydrin with an acyl halide such as acetyl or benzoyl chloride.  In the case where R is an aromatic carbamyl radical, the thiazyl 1-thio methylene hydrin is reacted with an aromatic iso-cyanate.  A large number of thiazyl 1-thio methylene hydrins are mentioned of which the following are typical alpha and beta naphtha thiazyl 1-thio methylene hydrins, the xylyl thiazyl 1-thio methylene hydrins, 4-nitro benzothiazyl 1-thio methylene hydrin, 5-nitro benzothiazyl 1-thio methylene hydrin, 4-chlor benzothiazyl 1-thio methylene hydrin, 4-nitro-5 chlor benzothiazyl 1-thio methylene hydrin, 3-phenyl benzothiazyl 1-thio methylene hydrin, 3-methyl-5-nitro benzothiazyl 1-thio methylene hydrin.  Typical acyl halides are propionyl chloride, paranitro benzoyl chloride, p-benzyl benzoyl chloride and iso butyryl chloride.  Typical aromatic isocyanates are ortho and para tolyl isocyanates, the xylyl isocyanates the cresyl isocyanates and the ortho and para anisyl isocyanates.  In examples: (1) acetyl chloride is reacted with benzothiazyl 1-thio methylene hydrin to give benzothiazyl 1-thio methylene acetate; (2) the corresponding benzoate is formed by using benzoyl chloride instead of acetyl chloride; (3) benzothiazyl 1-thio methylene hydrin is reacted with phenyl isocyanate to give benzothiazyl 1-thio methylene phenyl carbamate; (4) the corresponding alpha naphthyl carbamate is formed by using alpha naphthyl isocyanate.  The accelerators of the present invention may be used either alone or in conjunction with basic nitrogen containing accelerators such as diphenylguanidine, 2 : 4-diamino diphenylmethane, butyl ammonium oleate, and urea salts.  The thiazyl 1-thiomethylene hydrins may be prepared by interacting formaldehyde and an alkaline solution of a 1-mercapto-benzothiazole, acidifying the reaction product, and separating the thiazyl 1-thio methylene hydrin.  As an example the preparation of benzothiazyl-1-thio-methylene hydrin is described.ALSO:The vulcanization of rubber is accelerated by the addition to the mix of a compound of the general formula T-S-CH2-O-R where T represents a 1-thiazyl radical, and R represents either an acyl group or an aromatic carbamyl radical.  In the case where R is an acyl radical, the compounds are preferably made by reacting a thiazyl 1-thio methylene hydrin with an acyl halide such as acetyl or benzoyl chloride.  In the case where R is an aromatic carbonyl radical, the thiazyl 1-thio methylene hydrin is reacted with an aromatic iso-cyanate.  A large number of thiazyl 1-thio methylene hydrins are mentioned of which the following are p  typical: alpha, beta naphthathiazyl 1-thio methylene hydrins, the xylyl thiazyl 1-thio methylene hydrins, 4-nitro-benzothiazyl 1-thio methylene hydrin, 5-nitro-benzothiazyl 1-thio methylene hydrin, 4-chloro benzothiazyl 1-thio methylene hydrin, 4-nitro-5-chlor benzothiazyl 1-thio methylene hydrin, 3-phenyl benzothiazyl 1-thio methylene hydrin, and 3 - methyl - 5 - nitro benzothiazyl 1 - thio methylene hydrin. Typical acyl halides are propionyl chloride p-nitro benzoyl chloride, p-benzyl benzoyl chloride, and iso butyryl chloride.  Typical aromatic isocyanates are o- and p-tolyl isocyanates, the xylyl isocyanates, the cresyl isocyanates and the o- and p-anisyl isocyanates.  In examples: (1) acetyl chloride is reacted with benzothiazyl 1-thio methylene hydrin to give benzothiazyl 1-thio methylene acetate; (2) the corresponding benzoate is formed by using benzoyl chloride instead of acetyl chloride; (3) benzothiazyl 1-thio methylene hydrin is reacted with phenyl isocyanate to give benzothiazyl 1-thio methylene phenyl carbamate; (4) the corresponding alpha naphthyl carbamate is formed by using alpha naphthyl isocyanate.  The accelerators of the present invention may be used either alone or in conjunction with basic nitrogen containing organic accelerators such as diphenylguanidine, 2 : 4-diamino-diphenylmethane, butyl ammonium oleate, and urea salts.