GB835826A - Improvements relating to reaction products of hydrocarbon dihalides and substituted phenylenediamines and their use in rubber - Google Patents

Abstract

The invention comprises the reaction product of a C1-C8 hydrocarbon dihalide where the halogen is chlorine, bromine or iodine and a substituted phenylenediamine of the formula R1R2NC6H4NHR3, in which R1, R2 and R3 are C1-C20 alkyl, cycloalkyl, alkylcycloalkyl or hydroxyalkyl groups, R2 may be hydrogen, and R1 and R2 may be joined as a C2-C10 alkylene group, and the phenylenediamine is the ortho or para isomer. The products may be of the following general formulae <FORM:0835826/IV (b)/1> <FORM:0835826/IV (b)/2> <FORM:0835826/IV (b)/3> where X is chlorine, bromine or iodine, and R's are as above. o- and p-Phenylenediamines which may be used in the preparation of the above compounds are the N,N1 dimethyl, diethyl, dipropyl, dibutyl, dioctyl and dicyclohexyl, N-methyl, N1-ethyl; N-ethyl, N1-butyl; N-methyl, N1-cyclohexyl; N,N-dimethyl-N1-hexyl; N,N - dimethyl - N1 - eicosyl; N,N1-dimethyl - N1 - undecyl; N,N - di - n - propyl-N1 - cyclohexyl; N,N1 - dimethyl - N1 - ethyl; N,N1 - dicyclohexyl N1 - methyl; N,N1 - di-amyl - N1 - octyl; N - methyl - N - ethyl, N1-isopropyl; N,N - dibutyl - N1 - sec. butyl; N,N - diethyl - N1 - sec. butyl; N,N1 - ethy-lene - N1 - (4 - hydroxy - 4 - methyl - 2 - hexyl); and N,N1 - (gamma - iso - amylpentamethylene) N1 - iso - propyl compounds. The last but one of the above compounds may be prepared by reacting ethylene dibromide with p-nitraniline and reducing the resulting condensate with iron and hydrochloric acid. The N,N-ethylene p-phenylenediamine so formed is then alkylated with 4 - hydroxy - 4 - methyl - 2 - pentanone, in ethanol and glacial acetic acid in the presence of Adam's platinum oxide catalyst, under hydrogen. The last of the above compounds may be prepared by condensing gamma picoline with i-butyraldehyde, and reducing the condensate with hydrogen and a nickel catalyst. The gamma-i-amylpiperidine so formed is then condensed with p-nitrochloro benzene, the condensate reduced with iron and hydrochloric acid, and the resulting N,N (gamma-i-amylpentamethylene) - p - phenylene diamine alkylated with acetone in the presence of hydrogen and Adam's catalyst. The other phenylenediamines mentioned are prepared from the appropriate N,N1 disubstituted phenylenediamine by reaction with the appropriate ketone in the presence of hydrogen and the platinum catalyst. Suitable hydrocarbon dihalides specified are methylene, propylene, butylene, tetramethylene, pentylene, hexamethylene, hexylene, octylene, methylethylene, pentamethylene and styrene dichloride and dibromide, ethylene, dichloride, dibromide, and diiodide, trimethylene dichloride, dibromide and bromoiodide, 1-chloro-2-bromoethane, 1,2, dibromocyclohexane, 1,2, and 1,3, dibromobutane; 1,4-dichlorobutene-2. Examples are given.ALSO:Compositions are described of a sulphur vulcanized rubber composition with an antiozone agent prepared by the condensation of a C1-C8 hydrocarbon dihalide with a substituted o- or p-phenylenediamine of formula R1R2NC6H4NHR3 where R1, R2 and R3 are alkyl, cycloalkyl, alkyl cycloalkyl, or hydroxyalkyl groups of 1-20 carbon atoms, R2 may also be hydrogen, and R1 and R2 may be joined as an alkylene group containing 2-10 carbon atoms. Halogens specified are chlorine, bromine and iodine. The rubbers used may be natural rubber, a polymer of butadiene or an alkyl derivative thereof, a copolymer of butadiene or an alkyl derivative thereof with a vinyl monomer, e.g. GR-S, or a mixture of any of these rubbers.