Patent GB-406379-A (GB)
Title: Improvements in or relating to the vulcanisation of rubber
IPC: C08K5/00
Filed: 1932-09-01
Abstract: Dithiocarbamate derivatives are prepared by reacting upon a salt of an inorganic or organic base with a dithiocarbamic acid, with a compound of the formula:--  <FORM:0406379/IV/1> wherein g  = chlorine or bromine and x = a substituted or unsubstituted amino group, or an ester group, the group OMe (Me = metal) or [OH, organic base]. Advantageously reaction is carried out in an aqueous or organic medium.  Accelerators from the following components have been prepared (A with B):--A: salts of the dithiocarbamic acids derived from ammonia, methylamine, b  - methoxyethylamine, butylamine, benzylamine, cyclohexylamine, aniline, toluidine, dimethylamine, dibutylamine, dibenzylamine, ethylcyclohexylamine, N-methylaniline, b -dimethoxyethylamine, pyrrolidine, piperidine, morpholine, thiomorpholine, dekahydroquinoline and perhydrocarbazole (these bodies are derived by reacting the bases with carbondisulphide and an inorganic base in molar proportions); B: esters of dichloro- or dibromoacetic acid with methanol, ethanol, propanol, glycol, glycolchlorhydrin, oxyethylamine, cyclohexanol, benzylalcohol (these are prepared by the customary esterification methods); the amides of dichloro- or dibromoacetic acid with ammonia, piperidine, methylamine, ethylamine, butylamine, xylidines, naphthylamines, dibutylamine, dibenzylamine, ethylaniline, morpholine, thiomorpholine, dicyclohexylamine.  (These amides are prepared by reacting the bases with the esters or halogenides of dihalogenacetic acid.)  Specification 353,871 is referred to.ALSO:The acceleration of the vulcanization of natural rubber and rubber-like masses is effected by adding a compound of the general formula <FORM:0406379/V/1> wherein R = hydrogen, alkyl, aralkyl or hydroaryl, R1 = hydrogen, alkyl, aryl, aralkyl or hydroaryl, or R and R1, jointly stand for a chain of alkylene groups which may be interrupted by a hetero-atom, and X = an amino group, which may be substituted, an ester group, the group 0Me (Me = metal) or [OH, organic amine]. Such compounds are prepared by reacting upon a salt of an inorganic or organic base with a dithiocarbamic acid, with a compound of the formula <FORM:0406379/V/2> \su = chlorine or bromine and X has the above significance. Advantageously reaction is carried out in an aqueous or organic medium.  Accelerators from the following components have been prepared and tested (A with B):-A: salts of the dithiocarbamic acids derived from ammonia, methylamine, b -methoxyethylamine, butylamine, benzylamine, cyclohexylamine, aniline, toluidine, dimethylamine, dibutylamine, dibenzylamine, ethylcyclohexylamine, N-methylaniline, b -dimethoxyethylamine, pyrrolidine, piperidine, morpholine, thiomorpholine, dekahydroquinoline and perhydrocarbazole (these bodies derived by reacting the bases with carbondisulphide and an inorganic base in molar proportion).  B: esters of dichloro- or dibromoacetic acid with methanol, ethanol, propanol, glycol, glycolchlorhydrin, oxyethylamine, cyclohexanol, benzylalcohol (these are prepared by the customary esterification methods); the amides of dichloro- or dibromoacetic acid with ammonia, piperidine, methylamine, ethylamine, butylamine, xylidines, naphthylamines, dibutylamine, dibenzylamine, ethylaniline, morpholine, thiomorpholine, dicyclohexylamine (prepared by reacting the bases with esters or halogenides of the dihalogenacetic acids).  The products are incorporated in the rubber mixes together with any other commonly used ingredients, fillers, pigments, softeners, anti-perishing agents &c., and preferably in some cases admixed with other accelerators such as diphenylguanidine or mercaptobenzythiazole.  Artificial rubber-like masses may be used with similar results.  Examples illustrate the accelerating properties of some of the compounds derived by reacting the above-listed components.  Specification 353,871 is referred to.