Patent GB-359267-A (GB)
Title: A method of treating rubber
IPC: C08K5/18
Filed: 1930-11-29
Abstract: Ketone-amine reaction products and derivatives thereof.-Rubber is treated, to retard deterioration, or to accelerate its vulcanization, with the reaction product of (1) a ketone and a salt of an aromatic amino compound, (2) a ketone and an aldehydearomatic amine condensation product, or (3) a ketone and an aromatic amino compound re-arranged in the presence of the same or another amino salt, or (4) with derivatives of such reaction products, e.g. aldehyde derivatives, sulphur derivatives, such as are formed by the action of sulphur, carbon disulphide, sodium polysulphides, and sulphur chlorides, derivatives obtained by the action of nitrous or formic acid, or naphthol addition products. In the reaction of ketones with aromatic amine salts, such aromatic amino compounds as contain at least one free o- or p-position are most suitable.  The reaction may be carried out, if desired, with the aid of a "dehydrating agent" of which are specified calcium chloride, iodine, sulphanilic acid, hydrochloric acid, sulphuric acid, phosphorus pentoxide, sodium hydroxide, magnesium perchlorate, acetic acid, barium oxide, zinc chloride, and the zinc chlorideamine double salt.  The preparation of the following reaction products is described in examples or referred to:  (a) ketone-amine salt products; acetone-aniline hydrochloride, mesityl oxideaniline hydrochloride, diacetone alcohol-aniline hydrochloride, acetone-diphenylguanidine hydro-chloride, acetone - p.p1 - diaminodiphenylmethane hydrochloride, acetone-di-o-tolylguanidine hydrochloride, acetone-o-tolylbiguanide hydrochloride, acetone-diphenylamine hydrochloride, acetone-phenyl-b -naphthylamine hydrochloride, acetone-aniline acetate, acetone-o-toluidine hydrochloride, acetone-o.o1-diaminodiphenylsulphide hydrochloride acetone - diphenylhydrazine hydrochloride.  (b) Ketone aldehyde amine products: acetone-acetaldehyde aniline condensation product.  (c) Ketoneamine rearranged reaction products: acetone-aniline rearranged with aniline hydrochloride, acetone-biphenylguanidine rearranged with aniline hydrochloride, acetone-a -or b -naphthalamine rearranged with aniline hydrochloride, acetone-4.41-diamino-diphenylamine rearranged with toluidine hydrochloride.  Instead of the ketones mentioned above there may be used phorone, diethyl ketone, benzophenone, acetophenone, dichloracetone, aldol acetone, alkyl acetone, benzal acetone, diacetyl, acetyl-acetone, acetonyl acetone, salicylaldehyde acetone, furfural acetone.  The term ketone is also further defined as including the corresponding thioketone or ketone dihalide. Instead of the aromatic amino compounds mentioned above there may be used monochloraniline, m- and p-toluidine, xyli-dines, a  and b -naphthylamine, aminodiphenyls, dinaphthylamines, asymmetric diphenylhydrazine, diaminodiphenyl sulphide, diaminodiphenyl polysulphides, diaminodinaphthyl sulphides, p-amino-benzylaniline, dinaphthyldiaminoethane, ditolyldiaminoethane, p - amino - p1 - naphthylaminodiphenylmethane,, p.p1 - diaminodiphenyldimethylmethane, p.p1-dinaphthylaminodiphenyldimethylmethane, phenyl-b -naphthylguanidine, phenyl-o-tolylguanidine, di-o-tolylbiguanide, monophenyl-biguanide, diphenylbiguanide, diphenylacetamidine, o-, m-, and p-phenylenediamine, dimethyl-p-phenylenediamine, m-toluylenediamine, benzidine, naphthylenediamine, 2.21- and 2.41-diamino-diphenyl, diphenyl, ditolyl and dinaphthyl-p-phenylenediamine, diphenylbenzidine, dinaphthylbenzidine, naphthyl and dinaphthyl-m-toluylene-diamine, 2.41- and 4.41-diaminodiphenylamine, or mixtures of any of the foregoing aromatic amino compounds with a phenol such as phenol, a -naphthol, b -naphthol.  (d) Derivatives of the foregoing reaction products: addition products of b -naphthol + acetone-p-p1-diaminodiphenyl-methane hydrochloride, b -naphthol + acetone-aniline hydrochloride, b -naphthol + acetone-aniline rearranged with aniline hydrochloride; the b -naphthol may be replaced by a -naphthol, methylene-di-b -naphthol, dihydroxynaphthalenes such as 1-5-dihydroxynaphthalene: reaction products of formaldehyde and acetone-aniline hydrochloride, formaldehyde and diacetone alcohol-aniline hydrochloride, formaldehyde and acetone-o-tolylbiguanide hydrochloride, formaldehyde and acetone-diphenylguanidine hydrochloride, formaldehyde and acetoneaniline rearranged with aniline hydrochloride; the formaldehyde may be replaced by acetaldehyde, aldol, butylaldehyde, crotonaldehyde or heptaldehyde. p.p1-Dinaphthylaminodiphenyldimethylmethane is prepared by reacting one mol. of p.p1-diaminodiphenyldimethylmethane with 2 mols. of b -naphthol in the presence of a dehydrating agent (calcium chloride or iodine).  Specification 359,773 is referred to.ALSO:Rubber is treated, to retard deterioration, or to accelerate its vulcanization, with the reaction product of a ketone and a salt of an aromatic amino compound, or of a ketone and an aldehyde-aromatic amine condensation product, or with a reaction product of a ketone and an aromatic amino compound rearranged in the presence of the same or another amino salt.  Derivatives of such products, e.g. aldehyde derivatives, sulphur derivatives such as are formed by the action of sulphur, carbon disulphide, sodium polysulphides, and sulphur chlorides, derivatives obtained by the action of nitrous acid, or formic acid or naphthol addition products may be used.  Salts are defined as meaning the acid addition product of the amino compound.  In the reaction of ketones with aromatic amine salts, such aromatic amino compounds as contain at least one o or p carbon atom linked to hydrogen are most suitable.  The reaction may be carried out if desired with a dehydrating agent such as calcium chloride, iodine, sulphanilic acid, hydrochloric acid, sulphuric acid, phosphorus pentoxide, sodium hydroxide, magnesium perchlorate, acetic acid, barium oxide, zinc chloride, &c.  Alternatively the zinc chloride double salt of the amine may be used.  Numerous examples of the preparation of these reaction products are given.  Specification 359,773 is referred to.