Patent GB-740537-A (GB)
Title: Improvements in or relating to new composition of matter and method of making the same
Inventor: HARMAN MARION WESLEY
IPC: C08K5/00
Filed: 1952-01-31
Abstract: The invention comprises diamino sulphides having the general formula <FORM:0740537/IV(a)/1> where R1 and R2 are methylene, alkylmethylene, polymethylene or alkylpolymethylene groups containing less than 5 carbon atoms and R3 and R4 are tertiary alkyl groups containing at least 8 carbon atoms or substituted alkyl groups in which the substituents are chloro, cyano, alkoxy, amino or N-cyanoalkylaminoalkyl groups, and x is an integer.  Such compounds are obtained by reacting a sulphur halide with an aminoalkyl nitrile having the formula NC-R1-NH-R3. Where R3 and R4 in the product are both N-cyanoalkylaminoalkyl groups the product can be reacted with an additional molecular proportion of a sulphur monohalide.  In examples: (1) one molecular proportion of di-(b -cyanoethyl) amine is reacted in benzene with 0.25 molecular proportion of sulphur monochloride, by-product amine hydrochloride is treated with sodium hydroxide, and the reaction then completed by the addition of a further 0.25 molecular proportion of sulphur monochloride and a further 0.5 mol. of sodium hydroxide, to give N,N,N1,N1-tetra-(b -cyanoethyl)-diamino disulphide; (2) 1 mol. of N,N1-di - (b  - cyanoethyl) - 1,6 - hexamethylene diamine (obtained by the reaction of 1 mol. of 1,6-hexamethylene diamine with 2 mols. of acrylonitrile in aqueous medium) is reacted with 0.5 mol. of sulphur monochloride to give N,N1 - di - (b  - cyanoethyl) - N,N1 - di - (o  - [b  - cyanoethylamino) - n - hexyl) - diamino disulphide which is further reacted with 0.5 mols. of sulphur monochloride in the presence of sodium hydroxide to give N,N1-di-(b -cyanoethyl - N(1),N1(6) - hexamethylenediamino disulphide of the formula <FORM:0740537/IV(a)/2> where n is 1 or 2 and probably 2; (3) one mol. of b  - tert. - octylaminopropionitrile is reacted with 0.25 mol. of sulphur monochloride, and after the addition of sodium hydroxide with a further 0.25 mol. to give N,N1-di-(b -cyanoethyl) - N,N1 - di - b  - tert. - octyldiamino disulphide.  Other compounds mentioned are the sulphides of b -tert.-decylaminopropionitrile, b -tert. - dodecylaminopropionitrile and b  - tert. - pentadecylaminopropionitrile.  The products are useful as vulcanization agents for rubber (see Group V).ALSO:As curing agents for rubber there are specified compounds of the formula <FORM:0740537/V/1> in which x is an integer and R1 and R2 are like or unlike methylene, alkylmethylene, polymethylene or alkylpolymethylene groups containing less than 5 carbon atoms and R3 and R4 are tertiary alkyl groups containing at least eight carbon atoms or substituted alkyl groups in which the substituents are chloro, cyano, alkoxy, amino or N-cyanoalkylaminoalkyl groups.  The preparation is described (see Group IV(b)) of N.N.N1.N1-tetra- (b -cyanoethyl)-diamino disulphide, N.N1-di (b -cyanoethyl)-N(1).N(6)-hexamethylenediamino disulphide having the formula <FORM:0740537/V/2> where n is 1 or 2, and probably 2, and of N.N1-di (b -cyanoethyl)-N.N1-di-b -tert. octyldiamino disulphide. Also mentioned are the sulphides of b -tert. decylaminopropionitrile, and b -tert. dodecylaminopropionitrile p and b -tert. pentadecylaminopropionitrile.  As an illustration: to a composition of smoked sheet rubber, carbon black, zinc oxide, mineral hydrocarbons softener, stearic acid para-amino-diphenyl-acetone reaction product, and N-cyclohexyl-2-benzothiazole there is added N.N.N1-N1-tetra-(b -cyanoethyl) diamino disulphide, and the mixture is cured by heating in a press at 292 DEG  F.