Patent GB-794073-A (GB)
Title: Nitrosoarylenediamines and compositions containing the same
Inventor: TUNG CHING CHEN
IPC: C08K5/32
Filed: 1956-03-07
Abstract: N-nitroso-N-arylarylene diamines of general formula <FORM:0794073/IV (b)/1> in which R is an aryl group, R1 is an arylene group, R2 is an aryl or aliphatic hydrocarbon group and one of R3 and R4 is a nitroso group, the other being either a hydrogen atom or nitroso group, are claimed as new substances. They are prepared by treating a hydrohalide of an arylene diamine of general formula R-NH-R1-NH-R2 with an alkali metal nitrite in the presence of water at room temperature or below.  The process may be carried out by dissolving or suspending the amine in an organic solvent, e.g. butanol, or glacial acetic acid, adding a hydrohalic acid such as hydrochloric acid in an amount slightly in excess of that theoretically required to form the hydrohalide of the amine and then gradually adding substantially the theoretical quantity of sodium nitrite, preferably as an aqueous solution, at a temperature below 20 DEG  C.  Examples are given of the preparation of N, N1-dinitroso-N-phenyl-N1-cyclohexyl-para phenylenediamine; N,N1 - dinitroso - N,N1 - diphenyl - para - phenylenediamine; N,N1 - dinitroso - N - cyclohexyl - N1 - b  - naphthyl - para-phenylenediamine; and mention made of N,N1 - dinitroso - N - para - tolyl - N1 - cyclohexyl - para - phenylenediamine; N - paramethoxyphenyl - N1 - cyclohexyl - para - phenylenediamine; N,N1 - dinitroso - N - phenyl - N1 - hexyl - para - phenylenediamine; N,N1 - dinitroso - N - phenyl - N1 - octyl - para - phenylenediamine; N - nitroso - N,N1 - diphenyl - para - phenylenediamine and N - nitroso - N - phenyl-N1 - cyclohexyl - para - phenylene - diamine.ALSO:As vulcanization controlling agents for synthetic rubbers there are used N-nitroso-N-arylarylene diamines of general formula: <FORM:0794073/IV (a)/1> in which R is an aryl group, R1 is an arylene group, R2 is aryl or aliphatic hydrocarbon group, and one of R3R4 is a nitroso group, the other being either a hydrogen atom or nitroso group. These compounds may be compounded with a sulphur vulcanizable rubber, e.g. synthetic diene polymers such as homopolymers of butadiene, isoprene, 2-3 dimethyl-butadiene and copolymers of these monomers with styrene, acrylonitrile and isobutylene, a vulcanizing agent for the rubber and a delayed action sulphenamide vulcanization accelerator.  Bis amino N,N1 sulphides, preferably the disulphides, e.g. bismorpholinyl N-N1 disulphide, bis tetrahydro thienylamino N,N1 disulphide and bis (b -cyanoethylamino) N-N1 disulphide are used in conjunction with N-nitroso-N-aryl arylene diamines as vulcanizing agents.  Vulcanization accelerators used are benzothiazole, or thiazole sulphenamides having an N-substituent which may be alkyl cycloalkyl or heterocyclic, e.g. N-cyclohexyl 2-benzothiazole sulphenamide, N-tertiary butyl 2-benzothiazole sulphenamide, N-(11 piperidino) 2-benzothiazole sulphenamide.ALSO:As vulcanization retarding agents for rubber there are used N-nitroso-N-arylarylene diamines of general formula:-  <FORM:0794073/V/1> in which R is an aryl group, R1 is an arylene group, R2 is aryl or aliphatic hydrocarbon group, and one of R3 and R4 is a nitroso group, the other being either a hydrogen atom or a nitroso group, e.g., N-N1 dinitroso-N-phenyl-N cyclohexyl para phenylene diamine.  These compounds may be compounded with a sulphur vulcanizable rubber, e.g., natural crude rubber, a vulcanizing agent for the rubber and a delayed action sulphenamide vulcanization accelerator. Bis-amino-N-N1 sulphides preferably the disulphides, e.g., bismorpholinyl N-N1 disulphide, bis tetra thienylamino N,N1 disulphide and bis (b -cyanoethylamino) N-N1 disulphide, are used in conjunction with the N-nitroso-N-aryl arylene diamines as vulcanizing agents.  The vulcanization accelerators are benzothiazole or thiazole sulphenamides having an N substituent which may be alkyl, cycloalkyl or a heterocyclic group, e.g., N-cyclohexyl 2-benzothiazole sulphenamide N-tertiary Butyl-2-benzothiazole sulphenamide, N-(11 piperidino) 2-benzothiazole sulphenamide, N, cyclopentamethylene 4-ethyl thiazole sulphenamide, 4(41-methyl-21-thiazolylmercapto) morpholine, 5-carbethoxy-N-isopropyl-4-methyl -2-thiazolesulphenamide and 4-methyl 2(41-morpholinyl-sulphenyl)-5-thiazole carboxylic acid amongst others.  Examples are given of rubber compositions, containing N-cyclohexyl N1-phenyl N-N1 dinitroso para-phenylenediamine, or N,N1 dinitroso N,N1 diphenyl paraphenylenediamine with N,-cyclohexyl 2-benzothiazole sulphenamide, Bismorpholinyl N-N-disulphide may be present.  Other rubber compositions mentioned are those containing N,N1 dinitroso N-N1 diphenyl-para-phenylenediamine with one of the following N-cyclohexyl-2-benzothiazole sulphenamide, 4-(2-benzothiazolysulphenyl) morpholine, or N-tertiary butyl 2-benzothiazole sulphenamide.  Smoked sheet rubber is used in preparing the compositions described in the examples.