Patent GB-422191-A (GB)
Title: Improvements in and relating to method of preparing rubber
IPC: C08K5/29
Filed: 1933-06-02
Abstract: The ageing of rubber is retarded by the addition to the mix of a substituted or unsubstituted amino derivative of a biphenylene oxide. Compounds mentioned are 2 : 7 diamino biphenylene oxide, obtained by nitrating biphenylene oxide and reducing with iron filings and hydrochloric acid, 2-amino biphenylene oxide obtained similarly from the mono-nitro compound.  2 : 7 di (methylene amino) biphenylene oxide, 2 (methylene amino) biphenylene oxide made by reacting formaldehyde and the corresponding unsubstituted amino derivative of biphenylene oxide.  Instead of formaldehyde, crotonaldehyde, acrolein, or aldol may be used.  Other compounds are 2 : 7 di (beta naphthyl amino) biphenylene oxide obtained by interacting beta naphthol and 2 : 7 diamino biphenylene oxide, or 2-amino biphenylene oxide.  Other phenolic compounds may be used instead of beta naphthol.  Finally, 2 (formyl amino) biphenylene oxide prepared by interaction of equimolecular quantities of formic acid and 2-amino biphenylene oxide.  Tests are given to show the activity of the compounds.  The Specification as open to inspection under Sect. 91 comprises also the use as antiagers of compounds of the general formula R--O--R, where R represents an aryl or amino substituted aryl group and R1 represents an amino substituted hydrocarbon group.  As an example, 2 : 4 diamino phenyl beta naphthyl ether prepared by reacting the sodium salt of beta naphthol with dinitro chlor benzene and reducing the product with iron filings and hydrochloric acid.  In addition to the diamino phenyl naphthyl ethers a long list of structurally related compounds is given of which 2 : 4 diamino-phenyl 3<1> acenaphthyl ether; para toluene bis (2 : 4 diaminophenyl ether); p isopropyl amino-p<1> amino d-m-tolyl ether and 4 : 4<1>-tetramethyldiaminodiphenyl ether are typical examples. Another type of compound falling within the above general formula is exemplified by beta anilido ethyl beta naphthyl ether, prepared by mixing an aqueous solution of beta naphthol in caustic soda with ethylene dichloride.  Two compounds result which are chlor ethyl beta naphthyl ether, and ethylene bis-beta naphthyl ether. The former is reacted with aniline in an autoclave to give the required compound. If ammonia is used instead of aniline, amino ethyl beta naphthyl ether is formed.  Other amines such as the xylidenes, piperidine cyclohexylamine butylamine and homologues thereof may be used.  In addition to the ethyl ethers mentioned above, the methyl, butyl, propyl) and amyl ethers are included. The invention also includes halogen alkyl aryl ether reaction products of the amino phenols, hydroxy substituted tolidines, propyl amines, ethyl amines and related compounds.  A long list of such reaction products is given of which typical examples are m-xylyl amino ethyl-beta naphthyl ether toloxyethyl tolylamine, benzidyl ethyl phenyl ether; and phenoxy methyl chlor phenyl amine.  This subject-matter does not appear in the Specification as accepted.ALSO:The ageing of rubber is retarded by the addition to the mix of a substituted or unsubstituted amino derivative of a biphenylene oxide.  Compounds mentioned are 2 : 7 diamino biphenylene oxide, obtained by nitrating biphenylene oxide and reducing with iron filings and hydrochloric acid, 2-amino-biphenylene oxide obtained in a similar way from the mono nitro compound, 2 : 7 di (methylene amino) biphenylene oxide, 2 (methylene-amino) biphenylene oxide made by reacting formaldehyde and the corresponding unsubstituted amino derivative of biphenylene oxide.  Instead of formaldehyde, crotonaldehyde, acrolein, or aldol may be used.  Other compounds are 2 : 7 di (beta naphthyl amino) biphenylene oxide and 2 (beta naphthyl amino) biphenylene oxide obtained by interacting beta naphthol and 2 : 7 diamino biphenylene oxide or 2-amino-biphenylene oxide.  Other phenolic compounds may be used instead of beta naphthol.  Finally, 2 (formyl amino) biphenylene oxide prepared by interaction of equimolecular quantities of formic acid and 2-amino biphenylene oxide.  Tests are given to show the activity of the compounds.  The Specification as open to inspection under Sect. 91 comprises also the use as antiagers of compounds of the general formula R-O-R1 where R represents an aryl or amino substituted aryl group and R1 represents an amino substituted hydrocarbon group.  In an example, 2 : 4 diamino-phenyl-beta naphthyl ether is prepared by reacting the sodium salt of beta naphthol with dinitro chlor benzene, and reducing the product with iron and hydrochloric acid.  In addition to the diamino phenyl naphthyl ethers a long list of structurally related compounds is given of which 2 : 4 diamino phenyl-31 acenaphthyl ether; para toluene bis (2 : 4 diamino phenyl ether); p-isopropyl amino p1-amino di-m-tolyl ether and 4 : 41 tetramethyldiaminodiphenyl ether are typical examples.  Another type of compound falling within the above general formula is exemplified by beta anilido ethyl beta naphthyl ether prepared by mixing an aqueous solution of beta naphthol in caustic soda with ethylene dichloride.  Two compounds result which are chlor ethyl beta naphthyl ether and ethylene bis-beta naphthyl ether.  The former is reacted with aniline in an autoclave to give the required compound.  If ammonia is used instead of aniline, amino ethyl beta naphthyl ether is formed.  Other amines such as the xylidines, piperidine, cyclohexylamine butylamine and homologues thereof may be used.  In addition to the ethyl ethers mentioned above the methyl, butyl, propyl and amyl ethers are included.  The invention also includes halogen alkyl aryl ether reaction products of the amino phenols, hydroxy substituted tolidines, propyl amines, ethyl amines and related compounds.  A long list of such reaction products is given, of which typical examples are m-xylyl amino ethyl-beta naphthyl ether; toloxy ethyl tolylamine; benzidyl ethyl phenyl ether; and phenoxy-methyl chlor phenyl amine.  This subject-matter does not appear in the Specification as accepted.