Patent GB-423514-A (GB)
Title: Improvements in or relating to the production and use of accelerators for vulcanisation processes
IPC: C08K5/00
Filed: 1933-08-03
Abstract: Products useful as accelerators for rubber vulcanization are obtained by treating an organic base (or aldehyde-ammonia reaction product) with a mercaptoarylthiazole, and reacting the product with a carboxylic acid halide.  In the examples: (1) hexamethylenetetramine (1 mol.) and mercaptobenzothiazole (1,5 mol.) are heated together and the product is treated with phthalyl chloride (about 0,5 mol.); (2) example 1 is modified by using about 1 mol. of phthalyl chloride; (3) the reaction product of hexamethylenetetramine and mercaptobenzothiazole is treated with benzoyl chloride; (4) the reaction product of hexamethylene-tetramine and mercaptobenzothiazole is treated with acetyl chloride; (5) mercaptobenzothiazole and acetaldehydeammonia are heated together, and the product is treated with phthalyl chloride; (6) mercaptobenzothiazole and butyraldehyde-ammonia are heated together, and the product is treated with benzoyl chloride; (7) triheptylidenediamine, (C7H14)3N2, prepared from 3 mols. of heptaldehyde and 2 mols. of ammonia, is heated with mercaptobenzothiazole, and the product is treated with phthalyl chloride; (8) the piperidine salt of mercaptobenzothiazole is treated with phthalyl chloride; or (9) with benzoyl chloride; (10) the salt from 4 : 4<1>-diaminodiphenylmethane and mercaptobenzothiazole is treated with phthalyl chloride.  Other organic bases which may be reacted with the mercaptoarylthiazole are diphenylguanidine, ethylideneaniline, diethylamine, dibenzylamine, triethanolamine, 2 : 4 - diaminodiphenylamine, p-phenylenediamine, aniline, 2-naphthylamine, morpholine, and anhydroformaldehydeaniline; mercaptotolylthiazoles and mercaptonaphthothiazoles may be used instead of mercaptobenzothiazole; other carboxylic acid halides which may be used are acetyl bromide, succinyl chloride, heptoyl chloride and benzoyl iodide.  Specification 400,991 is referred to.ALSO:Products useful as accelerators for rubber vulcanization are obtained by treating an organic base (or an aldehyde-ammonia reaction product) with a mercaptoarylthiazole, and reacting the product with a carboxylic acid halide.  The accelerators may be incorporated in a rubber mix alone or together with a basic organic nitrogenous accelerator.  In the examples, (1) hexamethylenetetramine (1) and mercaptobenzothiazole (1,5 mol.) are heated together and the product is treated with phthalyl chloride (about 0,5 mol.); (2) example 1 is modified by using about 1 mol. of phthalyl chloride; (3) the reaction product of hexamethylenetetramine and mercaptobenzothiazole is treated with benzoyl chloride; (4) the reaction product of hexamethylenetetramine and mercaptobenzothiazole is treated with acetyl chloride; (5) mercaptobenzothiazole and acetaldehyde-ammonia are heated together and the product is treated with phthalyl chloride; (6) mercaptobenzothiazole and butyr-aldehyde-ammonia are heated together, and the product is treated with benzoyl chloride; (7) triheptylidenediamine, (C7H14)3N2, prepared from 3 mols. of heptaldehyde and 2 mols. of ammonia, is heated with mercaptobenzothiazole, and the product is treated with phthalyl chloride; (8) the piperidine salt of mercaptobenzothiazole is treated with phthalyl chloride or with benzoyl chloride; (9) the salt from 4 - 41-diaminodiphenylmethane and mercaptobenzothiazole is treated with phthalyl chloride. Diphenylguanidine may be added to the mix used in any of the preceding examples; each example includes details of the properties of the cured product.  Other organic bases which may be reacted with the mercaptoarylthiazole are diphenylguanidine, ethylideneaniline, diethylamine, dibenzylamine, triethanolamine, 2 : 4-diaminodiphenylamine, p-phenylenediamine, aniline, 2-naphthylamine, morpholine, and anhydroform aldehydeaniline; mercaptotolylthiazoles and mercaptonaphthothiazoles may be used instead of mercaptobenzothiazole; other carboxylic acid halides which may be used are acetyl bromide, succinyl chloride, heptoyl chloride and benzoyl iodide; other additional accelerators, which may replace the diphenylguanidine used in the examples, are di-o-tolylguanidine, phenylhydrazine, piperazine and anhydroformaldehydeaniline. Specification 400,991 is referred to.