Patent GB-488138-A (GB)
Title: Improvements in the vulcanization of rubber
IPC: C08K5/48
Filed: 1937-07-29
Abstract: The vulcanization of rubber is accelerated by the addition to the mix of a thiazyl-2 selenide compound.  These compounds are characterized by the presence of the groupings <FORM:0488138/IV/1> Attached to the open bonds of the adjacent carbon atoms of the thiazole ring may be hydrogen, or aliphatic or aromatic radicals. The preferred embodiment is the inclusion of these two carbon atoms as part of an arylene radical such as phenylene, nitrophenylene and naphthalene radicals. Attached to the open bond of the selenyl selenium atom may be hydrogen or any organic or inorganic radical such as salt or ester forming radicals.  The compounds are such that by hydrolysis, double decomposition, rearrangement of the atoms in the molecule, or by the application of heat, they form the free selenyl compound or its diselenide. Compounds within the scope of the invention are 2-selenyl thiazoles such as 2-selenyl benzothiazole, the dithiazyl selenides such as di(benzothiazyl) di-selenide, and di(benzothiazyl) monoselenide; the metal salts of the 2-selenyl thiazoles such as the zinc, lead, cadmium, mercury, sodium, potassium and barium salts of 2-selenyl benzothiazole; the reaction products of alkali metal salts of the 2-selenyl thiazoles with chlorinated organic compounds such as the reaction products of sodium benzothiazyl-2-selenide with the orthonitrochlorbenzenes, and the ortho nitro phenyl sulphur halides such as 2-benzoyl ortho nitrophenyl sulphur bromide, and 2-nitrophenyl sulphur chloride; with the aromatic acyl halides such as benzoyl chloride and phthaloyl chloride; with the furoyl and tetrahydro furoyl halides; with chlorinated ketones such as mono-and dichlor acetone and p  acetophenone; with the mono- and dichlor acetamides, with chlor benzothiazole and with benzal chloride.  Also the reaction products of 2-selenyl benzothiazole with formaldehyde, with amines such as ortho and para toluidine ortho and para phenetidines, anisidine and alpha and beta naphthylamines with the guanidines such as diphenylguanidine and di-o-tolylguanidine, with aldehyde amines such as ethylidene-aniline, crotonylidene aniline and hexamethylene tetramine.  Nitroso derivatives may be made by the action of gaseous ethyl nitrite on arylaminomethylene - benzothiazyl 2 - selenides.  Other compounds are the reaction products of sodium thiazyl-2-selenides, particularly sodium benzothiazyl-2-selenide with aryl seleno halides such as o-nitrophenyl seleno chloride and phenyl seleno chloride; with quinoline; with the reaction product of benzal chloride and hexamethylene tetramine, with carbonyl chloride to give dibenzothiazyl diseleno carbonate, with thiophosgene to give a corresponding product, with quaternary ammonium halides such as hexadecyl pyridinium chloride, hexadecyl-trimethyl-ammonium bromide benzyl trimethyl ammonium chloride, benzyl pyridine ammonium chloride, betahydroxyethyl pyridine chloride, N-chloro-piperidine, N-chloro-morpholine, dimethyl chloramine, dibutyl - chloramine, diphenyl carbamine chloride, imino-methylene dichlorides and dichlor-di-imides.  Still other compounds are the reaction products of sodium-5-nitro-benzo-thiazyl-2-selenide with 2-chlorquinoline, benzo-thiazyl - 2 - seleno - methylene hydrin with acetylchloride. Others are the reaction products of formaldehyde with 2-selenyl thiazoles and the reaction product of methylol guanidines with the 2-selenyl thiazoles such as the reaction product of 2-selenyl benzothiazole with the reaction product of diphenylguanidine and formaldehyde.  In examples: (1) 2-selenyl benzothiazole is prepared by the action of sodium selenide or hydro-selenide on 2-chlor benzothiazole; (2) 2-selenyl benzothiazole is oxidized to di(benzothiazyl) diselenide by such oxidizing agents as iodine, hydrogen peroxide and ammonium persulphate; (3) bivalent metal salts of the 2-selenyl thiazoles are prepared by adding a solution of a soluble salt of the desired metal to an aqueous solution of an alkali metal salt of the 2-selenyl thiazole, the zinc lead mercuric and cadmium salts are described as examples 3, 4, 5 and 6.  Organic salts described in examples 7 and 8 are the piperidine and the diphenylguanidine salts; (9) 2-selenyl benzothiazole formaldehyde and urea are reacted together; (10) sodium benzothiazyl 2-selenide is reacted with 2 : 4-dinitro chlor benzene.  Examples 11-14 describe the addition products of zinc benzothiazyl 2-selenide with piperidine, cyclohexylamine, benzylamine, and di-amylamine respectively.  Other amines are also mentioned; (15) 2-selenyl benzothiazole is reacted with benzoyl chloride, other acyl halides are also mentioned; (16) 2-selenol benzothiazole is reacted with 2-chlor benzothiazole; (17) 2-selenyl benzothiazole is reacted with formaldehyde and piperidine; (18) as example (17) using aniline instead of piperidine.  Examples are given to show the efficiency of the accelerators in a standard rubber mix.ALSO:The vulcanization of rubber is accelerated by the addition to the mix of a thiazyl-2-selenide compound.  These compounds are characterized by the presence of the grouping <FORM:0488138/V/1> Attached to the open bands of the adjacent carbon atoms of the thiazole ring may be hydrogen, or aliphatic or aromatic radicals. The preferred embodiment is the inclusion of these two carbon atoms as part of an arylene radical such as phenylene, nitrophenylene and naphthalene radicals. Attached to the open bond of the selenyl selenium atom may be hydrogen or any organic or inorganic radical such as salt or ester forming radicals.  The compounds are such that by hydrolysis, double decomposition, rearrangement or by the application of heat, they form the free selenyl compound or its diselenide.  Compounds within the scope of the invention are 2-selenyl thiazoles such as 2-selenyl benzothiazole, the dithiazyl selenides such as di (benzothiazyl) diselenide and di(benzothiazyl) mono selenide; the metal salts of the 2-selenyl thiazoles, such as the zinc, lead, cadmium, mercury, sodium, potassium and barium salts of 2-selenyl benzothiazole; the reaction products of alkali metal salts of the 2-selenyl thiazoles with chlorinated organic compounds such as the reaction products of sodium benzothiazyl-2-selenide with the ortho nitro chlor benzenes, and ortho nitro phenyl sulphur halides such as 2-benzoyl-ortho nitro phenyl sulphur bromide, and 2-nitrophenyl sulphur chloride; with the aromatic acyl halides such as benzoyl chloride and phthaloyl chloride; with the furoyl and tetrahydrofuroyl halides; with chlorinated ketones such as mono- and dichlor-acetone and acetophenone; with the mono and dichlor acetamides, with chlor benzothiazole and with benzal chloride.  Also the reaction products of 2-selenyl benzothiazole with formaldehyde, with amines such ortho and para toluidine, ortho and para phenetidines, anisidine, and alpha- and beta-naphthylamines, with the guanidines such as diphenylguanidine and di-orthotolyguanidine with aldehyde amines such as ethylidene aniline, crotonylidene-aniline and hexamethylenetetramine.  Nitroso derivatives may be made by the action of gaseous ethyl nitrite on aryl amino methylene benzothiazyl-2-selenides.  Other compounds are the reaction products of sodium thiazyl-2-selenides, particularly sodium benzothiazyl-2-selenide with aryl seleno halides such as ortho nitro phenyl seleno chloride and phenyl seleno chloride; with quinoline, with the reaction product of benzal chloride and hexamethylene tetramine, with carbonyl chloride to give dibenzothiazyl diseleno carbonate, with thiophosgene to give a corresponding product; with quaternary ammonium halides such as hexadecyl-pyridinium chloride, hexadecyl-trimethyl-ammonium bromide, benzyl trimethyl ammonium chloride, benzyl pyridine ammonium chloride, betahydroxyethyl pyridine chloride, N-chloropiperidine, N-chloro morpholine, dimethyl chloramine, dibutyl chloramine, diphenyl carbamine chloride, imino methylene dichlorides and dichlor di-imides.  The other compounds are the reaction products of sodium-5-nitrobenzothiazyl-2-selenide with 2-chlor quinoline, benzothiazyl-2-seleno methylene hydrin with acetyl chloride.  Others are the reaction products of formaldehyde with 2-selenyl thiazoles and the reaction product of methylol guanidines with the 2-selenyl thiazoles such as the reaction product of 2-selenyl benzothiazole with the reaction product of diphenylguanidine and formaldehyde.  Numerous examples of the preparation of these compounds are given.  Examples are also given to show the efficiency of the accelerators in a standard rubber mix.