Patent GB-454863-A (GB)
Title: An improved method of vulcanizing rubber
IPC: C08K5/00
Filed: 1935-04-06
Abstract: The vulcanization of rubber is accelerated by incorporating therein compounds of the formula <FORM:0454863/IV/1> in which R is an arylene group, R1 is a radical containing a furane ring and R2 is any monovalent organic radical other than an alicyclic group.  These accelerators may be produced by reacting a 2-halogen-aryl-thiazole with a secondary furyl- or furfuryl-dithiocarbonate. 2-Halogen-aryl-thiazoles specified are the 2-chlor-6-nitro-, 2-chlor-6-methoxy-, 2-chlor-, 2-chlor-4-methyl-, 2-chlor-5-nitro; 2-chlor-6-ethoxy, 2-chlor-6-methyl-, 2-chlor-dimethyl-, 2-chlor-5- or 6-chlor-, 2-chlor-4-phenyl-, 2-chlor-5-chlor-6-nitro-, and 2-chlor-4-methyl-6-nitro-benzothiazoles; 2-chlor-naphtho-thiazoles and their nitro derivatives.  2-Chlor-benzothiazole may be prepared by the process disclosed in Specification 302,142, [Class 2 (iii)]; other 2-chlor-aryl thiazoles may be prepared similarly using the appropriate mercaptoaryl thiazole.  Other 2-halogen-aryl-thiazoles, e.g. the bromine compounds, may be prepared by a similar method using the desired sulphur halide in place of chlorine.  Dithiocarbonates specified are the potassium di-(a -furfuryl); sodium di-(a -furfuryl), sodium N-ethyl-a -furfuryl, potassium N-ethyl-a -furfuryl, sodium N-methyl-a -furfuryl, potassium N-phenyl-a -furfuryl, sodium N-isobutyl-a -furfuryl, ammonium N-n-propyl-a -furfuryl, ammonium N-isoamyl-a -furfuryl, sodium-a -furfuryl-N-benzyl, ammonium N-n-butyl-a -furfuryl and sodium N-b -phenylethylene-a -furfuryl dithiocarbonates; calcium and barium dithiocarbonates are also referred to.  The dithiocarbonates may be prepared by condensing the desired secondary amine with carbon disulphide in the presence of an alkali, e.g. sodium, potassium or ammonium hydroxide.  An accelerator specified is the reaction product of 2-chlor-6-nitro-benzothiazole and the sodium salt of di-(a -furfuryl) dithiocarbonate, it may be prepared by refluxing 2-chlor-6-nitro-benzothiazole, di-a -furfurylamine, carbon disulphide and sodium hydroxide in ethyl alcohol.  According to the Specification as open to inspection under Sect. 91, R2 may be an alicyclic group; the Specification refers to the use of sodium N-decahydro-b -naphthyl-a -furfuryl and potassium N-hexahydro-p-tolyl-a -furfuryl dithiocarbonates in the production of the accelerators.  This subject-matter does not appear in the Specification as accepted.ALSO:The vulcanization of rubber is accelerated by incorporating therein compounds of the formula <FORM:0454863/V/1> in which R is an arylene group, R1 is a radical containing a furane ring and R2 is any monovalent organic radical other than an alicyclic group.  These accelerators, may be produced by reacting a 2-halogen aryl thiazole with a secondary furyl or furfuryl dithiocarbonate.  2-halogen aryl thiazoles specified are the 2-chlor 6-nitro, 2-chlor 6-methoxy, 2-chlor, 2-chlor 4-methyl, 2-chlor 5-nitro, 2-chlor 6-ethoxy, 2-chlor 6-methyl, 2-chlor dimethyl, 2-chlor 5- or 6-chlor, 2-chlor 4 phenyl, 2-chlor 5-chlor 6-nitro and 2-chlor 4 methyl 6-nitro benzothiazoles; 2-chlor naphtho thiazoles and their nitro derivatives.  2-chlor benzothiazole may be prepared by the process disclosed in Specification 302,142, [Class 70], other 2-chlor aryl thiazoles may be prepared similarly using the appropriate mercaptoaryl thiazole.  Other 2-halogen arylthiazoles, e.g. the bromine compounds may be prepared by a similar method using the desired sulphur halide in place of chlorine.  Dithiocarbonates specified are the potassium di-(a -furfuryl); sodium-di-(a -furfuryl), sodium N-ethyl-a -furfuryl, potassium N - ethyl - a  - furfuryl, sodium N - methyl - a  - furfuryl, potassium N - phenyl - a - furfuryl, sodium N - isobutyl - a  - furfuryl, ammonium N - n - propyl - a  - furfuryl, ammonium N - isoamyl - a  - furfuryl, sodium - a  - furfuryl - N - benzyl, ammonium N-n-butyl-a -furfuryl and sodium N - b  - phenyl - ethylene - a  - furfuryl dithiocarbonates; calcium and barium dithiocarbonates are also referred to.  The dithiocarbonates may be prepared by condensing the desired secondary amine with carbon disulphide in the presence of an alkali, e.g. sodium, potassium or ammonium hydroxide.  An accelerator specified is the reaction product of 2 - chlor - 6 - nitro - benzothiazole and the sodium salt of di-(a -furfuryl)-dithiocarbonate, it may be prepared by refluxing 2-chlor-6-nitrobenzothiazole, di-a -furfuryl amine, carbon disulphide and sodium hydroxide in ethyl alcohol.  According to the Specification as open to inspection under Sect. 91, R2 may be an alicyclic group; the Specification refers to the use of sodium N - decahydro - b  - naphthyl - a  - furfuryl and potassium N - hexahydro - p - tolyl - a  - furfuryl dithiocarbonates in the production of the accelerators.  This subject-matter does not appear in the Specification as accepted.