Patent GB-909103-A (GB)
Title: Rubber antiozonant compounds and compositions containing them
IPC: C08K5/18
Filed: 1960-09-13
Abstract: Compounds of the formula <FORM:0909103/IV(a)/1> where R1 is an alkyl, cycloalkyl, or aryl radical, at least one R1 being alkyl or cycloalkyl, and where Z is a divalent hydrocarbon radical, and n is an integer from 1 to 10, are incorporated as antiozonants in natural or synthetic rubber compositions.  The method of treating cured rubber products as claimed in Specification 873,123 is excluded.  R1 in the general formula may be methyl, ethyl, butyl, amyl, octadecyl, cyclohexyl, cyclopentyl, phenyl, tolyl, xylyl, or naphthyl.  Many substituted p-phenylene diamines of the specified general formula are specified including N.N1-bis-(sec. butyl)-N.N1-bis-2-hydroxyethyl or propyl)-p-phenylene diamine, N.N1-bis[3-(5-methyl) heptyl]-N.N1-bis-(2-hydroxyethyl)-p-phenylene diamine, and reaction products of N.N1-bis[3-(5-methyl) heptyl]-p-phenylene diamine with 5.8 moles of ethylene oxide and of N-phenyl-N1-cyclohexyl-p-phenylene diamine with 4 moles of ethylene oxide.  Synthetic rubbers in which the compounds of the invention may be incorporated include butadiene polymers such as styrenebutadiene rubber, polyisoprene, butadiene-acrylonitrile elastomers, polychloroprene, polyisobutylene, polysulphide rubbers, silicone rubbers, and fluoroelastomers.  The proportion of the antiozonant incorporated may be 0,5-5,0% based on the weight of rubber.  The rubber compositions may contain additional ingredients such as zinc oxide, black pigment, stearic acid, petroleum softener, sulphur, N-cyclohexyl-2-benzothiazyl sulphenamide, bis-(2-mercaptobenzothiazolyl) disulphide, calcium carbonate, and titanium dioxide.ALSO:The invention comprises compounds of the formula <FORM:0909103/IV (b)/1> where R1 is an alkyl, cycloalkyl, or aryl radical, provided that at least one R1 is alkyl or cycloalkyl, and where Z is a divalent hydrocarbon radical, and n is an integer from 1-10, and their use as antiozonants in natural or synthetic rubber compositions.  The compounds as claimed in Specification 873,123 are disclaimed.  The compounds of the invention may be obtained by reacting an alkylene or aralkylene oxide with an appropriate N.N1-disubstituted p-phenylene diamine.  Examples of p-phenylene diamine starting materials are N-alkyl-N1-alkyl derivatives in which the alkyl groups are methyl, ethyl, propyl, butyl, amyl, octyl, decyl, and octadecyl, N.N1-dicycloalkyl derivatives such as N-cyclohexyl-N1-methylcyclohexyl derivatives; N-sec.butyl-N1-methylcyclohexylp-phenylene diamine; N-alkyl-N1-aryl-p-phenylene diamines where the aryl radicals may be phenyl, tolyl, xylyl, or naphthyl; N-tolyl-N1-cyclopentyl, N-phenyl-N1-undecyl and similar derivatives.  Examples of alkylene and aralkylene oxides are oxides of ethylene, propylene, butylenes, amylenes, styrene, naphthylstyrenes, and butadiene.  The reaction may be carried out at temperatures between 25 DEG  and 250 DEG C. under autogenous pressure. Solvents and catalysts may be present.  Examples describe the production of the N.N1-bis-(sec.-butyl)-N.N1-bis-(2-hydroxypropyl), the N.N1 - bis[3 - (5 - methyl)heptyl] - N.N1-bis(2-hydroxyethyl)-, and the N.N1-bis(sec.butyl)-N.N1-bis(2-hydroxyethyl) derivatives of p-phenylene diamine, and the preparation of reaction products of N.N1-bis[3-(5-methyl) heptyl]-p-phenylene diamine with 5.8 moles of ethylene oxide and of N-phenyl-N1-cyclohexyl-p-phenylene diamine with 4 moles of ethylene oxide.