Ether and thioether derivatives of n,n-substituted-p-phenylenediamines

摘要

The invention comprises polymers containing the repeating units where R1 is alkyl, alkenyl or cycloalkyl, containing not more than 12 carbon atoms, Z is C1 to C4 alkylene and X is oxygen or sulphur, which may be prepared by reacting in 1:1 molar ratio a p-phenylene diamine of the formula with a dihaloalkyl ether or thioether of the formula YZXZY where Y is chlorine, bromine or iodine. A solution of the ether in an inert solvent is added to a stirred solution of the diamine containing an acid acceptor at 0 DEG to 30 DEG C., then the mass is heated at 50 DEG to 80 DEG C. Elastomeric materials are stabilized against attack by oxygen or ozone by incorporating therein between 0,5 to 10% based on the weight of elastomer of a compound of the formula where R1, X and Z are as defined above, R2 is hydrogen or an R1 or -Z-X-R3 radical, R3 is an R1 or radical, with the proviso that when R2 is H or R1, then R3 is not R1. Elastomers mentioned are natural rubber and synthetic rubbers such as styrene-butadiene rubber, polyisoprene, butadiene-acrylonitrile elastomers, cis-polybutadiene, cis-polyisoprene, polysulphide rubbers, silicone rubbers, polychloroprene, polyisobutylene rubber and fluoro elsatomers. Detailed examples are given.ALSO:The invention comprises compounds of the formula where each R1 is an alkyl, alkenyl or cycloalkyl radical containing not more than 12 carbon atoms, R2 is hydrogen or an R1 or -Z-X-R2 radical, R2 is an R1 or radical, with the proviso that when R2 is hydrogen or an R1 radical, then R3 is a radical, Z is an alkylene radical containing 1 to 4 carbon atoms and X is oxygen or sulphur. Compounds in which R2 is R3-X-Z where R3 is R1 are made by reacting, in the presence of an inert solvent and a hydrogen halide acceptor, a p-phenylenediamine of the formula R1NH-C6H4, NHR1 with one or more haloalkyl ethers or thioethers of the formula R1XZY where Y is chlorine, bromine or iodine, the haloalkyl ether or thioether being used in an amount of at least 2 moles per mole of p-phenylenediamine reactant. Temperatures may be 50 DEG to 200 DEG C. Compounds in which R3 is are made by reacting 2 moles of the p-phenylenediamine reagent per mole of an ether or thioether of the formula YZXZY where Y is chlorine, bromine or iodine. By altering the proportion of reactants, compounds of different structures are obtained, and when a 1 : 1 molar ratio is used, polymeric compounds, or in high dilution ring compounds, are formed. Detailed examples are given.