Patent GB-395322-A (GB)
Title: Improvements in or relating to the treatment of rubber or like vucanizable materials
IPC: C08K11/00
Filed: 1931-10-06
Abstract: The ageing of rubber is retarded by adding to the mix a derivative of the reaction product of an aliphatic ketone and a secondary aromatic amino compound.  The term aliphatic ketone includes saturated and unsaturated aliphatic ketones of the open chain and cyclo-aliphatic series, as well as hydroxyl and halogen substituted derivatives of such ketones, and ketones obtained by condensation of the foregoing with aldehydes and ketones.  The term secondary amino compound includes broadly any aromatic amino compound which comprises at least one secondary amino nitrogen atom linked to an aromatic nucleus. Derivatives of the condensation products of amines and ketones that are employed are their nitroso derivatives and their reaction products with naphthols, sulphur, formic acid, and aldehydes. Ketone-amine reaction products mentioned as being suitable are acetone-diphenylamine, acetone-phenyl-a -naphthylamine, acetone - phenyl - b  - naphthylamine, acetone-diphenylethylene diamines, acetone-monoethylaniline, methyl ethyl ketonephenyl-a -naphthylamine, mesityloxide-phenyl-a -naphthylamine, acetone-diphenylformamidine, mesityloxide-phenyl-b -naphthylamine, acetone-di-o-tolylguanidine, acetone-diphenylguanidine, acetone-p-p<1>-di(naphthylamino)diphenylmethane, acetone - o - tolylbiguanide.  Other ketones which may be used are phorone, diethylketone, monochloracetone, dichloracetone, aldolacetone, diacetyl, acetyl-acetone, acetonyl acetone, di-acetone alcohol, ethylidene acetone, allyl acetone, aceto-phenones, benzalacetone, furfural acetone, salicyl aldehyde-acetone, cyclopentanone, and cyclohexanone.  Other secondary amino compounds are dinaphthylamines, naphthylaminodiphenyl, carbazole, p-nitrodiphenylamine, 2 : 4-dinitrodiphenylamine, p-aminodiphenylamine, p-hydroxydiphenylamine, sym-diphenyl-p-phenylenediamine, p-aminobenzylaniline, p-amino - p<1> - dinaphthylaminodiphenylmethane, sym-dinaphthyl-p-phenylenediamine, phenyl-b -naphthylguanidine, phenyl-o-tolylguanidine, di-o-tolylbiguanide, monophenylbiguanide and di-phenylbiguanide.  The ketone-amine reaction products may be formed with or without the aid of a dehydrating agent such as iodine, hydrochloric acid, calcium chloride, sulphanilic acid, phosphorus pentoxide, sodium hydroxide, magnesium perchlorate, acetic acid, barium oxide, zinc chloride, or amine addition products with zinc chloride such as ZnCl2(C6H5NH2). Examples are given of the preparation of (1) an acetone-diphenylamine condensation product prepared in the presence of iodine or hydrochloric acid; (2) an acetone-phenyl-p-naphthylamine condensation product prepared in the presence of iodine; (3) an acetone-phenyl-a -naphthylamine condensation product prepared in the presence of iodine; (4) a condensation product of b -naphthol with the product of example (1); (5) a nitrosoderivative of the product of example (1); (6) a reaction product of sulphur and the product of example (1); (7) a reaction product of formic acid and the product of example (1); (8) condensation products of formaldehyde with the product of example (1); and (9) condensation products of the product of example (1) with acetaldol and butyraldehyde.  Reference is made also to the reaction on the product of example (1) with acetaldehyde, paraldehyde, crotonaldehyde, and heptaldehyde, and to the production of sulphurized derivatives of the ketone-amine condensation products with the aid of carbon bisulphide or sodium polysulphide or sulphur chlorides.ALSO:The ageing of rubber is retarded by adding to the mix a derivative of the reaction product of an aliphatic ketone and a secondary aromatic amino compound.  The term aliphatic ketone includes saturated and unsaturated aliphatic ketones of the open chain and cyclo-aliphatic series, as well as hydroxyl and halogen substituted derivatives of such ketones, and ketones obtained by condensation of the foregoing with aldehydes and ketones.  The term secondary amino compound includes broadly any aromatic amino compound which comprises at least one secondary amino nitrogen atom linked to an aromatic nucleus.  Derivatives of the condensation products of amines and ketones that are employed are their nitroso derivatives and their reaction products with naphthols-, nitroso-, sulphur-, formic acid-, and aldehyde derivatives.  Ketone-amine reaction products mentioned as being suitable are acetone-diphenylamine, acetone-phenyl-a -naphthylamine, acetone-phenyl b -naphthylamine, acetone-diphenyl-ethylene diamines, acetone-monoethylaniline, methyl ethyl ketone-phenyl-a -naphthylamine, mesityloxide-phenyl-a -naphtylamine, acetone-diphenylformamidine, mesityloxide-phenyl-b -naphthylamine, acetone - di - o - tolylguanidine, acetone-diphenylguanidine, acetone-p-p1 di-(naphthylamino)diphenylmethane, acetone-o-tolylbiguanide. Other ketones which may be used are phorone, diethylketone, monochlor-acetone, dichloracetone, aldolacetone, diacetyl, acetyl-acetone, acetonyl acetone, di-acetone alcohol, ethylidene acetone, allyl acetone, aceto-phenones, benzal - acetone, furfural acetone, salicyl aldehyde-acetone, cyclopentanone, and cyclohexanone. Other secondary amino compounds are dinaphthylamines, naphthylaminodiphenyl, carbazole, p-nitrodiphenylamine, 2 : 4-diphenylamine, p-aminodiphenylamine, p-hydroxydiphenylamine, sym-diphenyl-p - phenylenediamine p - aminobenzylaniline, p-amino-p1-dinaphthylaminodiphenylmethane, sym - dinaphthyl - p - phenylenediamine, phenyl-b -naphthylguanidine, phenyl-o-tolylguanidine, di-o-tolylbiguanide, monophenylbiguanide and diphenylbiguanide.  The ketone-amine reaction products may be formed with or without the aid of a dehydrating agent such as iodine, hydrochloric acid, calcium chloride, sulphanilic acid, phosphorous pentoxide, sodium hydroxide, magnesium perchlorate, acetic acid, barium oxide, zinc chloride, or amine addition products with zinc chloride such as ZnCl2(C6H5NH2).  Numerous examples of the preparation of these reaction products are given, together with tests showing the effect of the addition of the products according to the invention to the mix.