Patent GB-957111-A (GB)
Title: Vulcanisation process and new vulcanisation accelerators
Inventor: AYAD KAMAL NAGUIB
IPC: C08K5/00
Filed: 1961-11-23
Abstract: The invention comprises aminomethyl halophenyl monosulphides in which the phenyl nucleus contains from 3-5 halogen atoms. Compounds as claimed per se are diethylaminomethyl pentachlorophenyl sulphide; piperidinomethyl pentachlorophenyl sulphide; morpholinomethyl pentachlorophenyl sulphide; 2, 6-Di-methyl - morpholinomethyl pentachlorophenyl sulphide.  In an example diethyl amino methyl pentachlorophenyl sulphide is prepared by reacting pentachlorothiophenyl, ethylamine and formaldehyde. In another example piperidinomethyl pentachlorophenyl sulphide is prepared by reacting pentachlorothiophenol with piperidine and formaldehyde. Other examples are given.ALSO:Natural and synthetic rubber (e.g. polymers of 1,3-butadiene for instance 1,3-butadiene itself, and copolymers of 1,3-butadienes with other monomers, such as styrene, acrylonitrile, isobutylene or methylmethacrylate) are vulcanised by incorporating an aminoaliphatic halophenyl sulphide in which the phenyl nucleus contains from three to five halogen atoms into unvulcanised rubber together with sulphur or a sulphur-containing vulcanising agent, and the mixture is heated to effect vulcanisation. The sulphide is generally a monosulphide but it can be one where the aminoaliphatic group is linked to the halophenyl group through a chain of two or more sulphur atoms and more than one aminoaliphatic group is linked through sulphur to a halophenyl nucleus, for instance the bis(aminomethylthio)halobenzenes, and those derived from polyamines, for instance the N,N1-bis(halo-phenylthiomethyl)diamines. The aliphatic group can be for instance an alkyl group, such as a methyl, ethyl, butyl or octyl group, a cycloalkyl group, such as a cyclopentyl or cyclohexyl group, or an aralkyl group, such as a benzyl group. Preferably the aliphatic group is a lower alkyl group, for instance one of not more than four carbon atoms, having either a straight or branched chain, for example, a methyl, ethyl, propyl, isopropyl, n-butyl or s-butyl group. The amino group can be primary, secondary (-NHR) or tertiary (-NRR1).  The groups R and R1 can each be aliphatic or aromatic or, in the group -NRR1, can together form a ring with the nitrogen atom for instance a piperidine, hexamethyleneimine or morpholine ring. The preferred aminoaliphatic halophenyl sulphides are those where R and R1 are each a lower alkyl or a cycloalkyl group, or where R and R1 form a ring with the nitrogen atom. Such compounds include the dimethylamino-diethylamino, di - n - propylamino-, di-s-butylamino-, cyclohexylmethylamino-, piperidino- and morpholino-aliphatic halophenyl sulphides. Specified sulphides are dimethylamino-methyl, 2,4,6-trichlorophenyl sulphide; diethyl-aminomethyl pentachlorophenyl sulphide; di-ethylaminomethyl pentafluorophenyl sulphide; di-n-propylaminomethyl 5-bromo-2, 4, 6-trichlorophenyl sulphide; N-cyclohexyl-N-methylaminomethyl pentachlorophenyl sulphide; diethylaminomethyltetrachloro -ptolyl sulphide; piperidinomethyl pentachlorophenyl sulphide; morpholinomethyl pentachlorophenyl sulphide; 2,6-dimethylmorpholinomethyl pentachlorophenyl sulphide; 2(diethylamino)ethyl pentachlorophenyl sulphide; 31-(dimethylamino) propyl 2,4,6-trichlorophenyl sulphide and 2-(di-n-butylamino)ethyl pentachlorophenyl sulphide. In the vulcanisation process the aminoaliphatic halophenyl sulphides are used as accelerators in conjunction with sulphur or a sulphur-containing vulcanising agent such as for instance an amine disulphide or a thiuram sulphide. The accelerator can be incorporated into the rubber using for example a roll mill or an internal mixer, together with conventional additives as required, such as for instance zinc oxide, stearic acid, the vulcanising agent, an antioxidant or a filler.