Patent GB-732928-A (GB)
Title: Improvements in and relating to the preservation of natural and synthetic rubber andrubber articles
Inventor: GOODMAN ISAAC
IPC: C08K5/13
Filed: 1952-12-03
Abstract: Synthetic rubber is preserved by incorporating an a ,b -bis-(2-hydroxy-5-methylphenyl)-ethane in which there is in the 3-position of each of the two phenyl radicals a substituent with not more than 8 carbon atoms chosen from the groups consisting of alkyl, cycloalkyl, and alkyl cycloalkyl.  The preferred substituted ethanes are 1,2-bis-(2-hydroxy-3-tert-butyl-5-methylphenyl) ethane, 1,2-bis-(2-hydroxy - 3 - tert - amyl - 5 - methyl phenyl) ethane, and 1,2-bis-(2-hydroxy-3-a -methyl cyclohexyl-5-methyl phenyl) ethane (see Group IV (b).  From 0.25 to 2.0 per cent based on the weight of the rubber is normally used.  In addition 1,2 - bis - (2 - hydroxy - 3,5 - dimethyl phenyl) ethane, 1,2-bis-(2-hydroxy-3-n-butyl-5-methyl phenyl) ethane, 1,2-bis-(2-hydroxy-3-sec. butyl-5-methyl phenyl) ethane, and 1,2-bis - (2 - hydroxy - 3 - cyclohexyl - 5 - methyl phenyl) ethane are specified.  The synthetic rubbers may be polymers of butadiene-1,3- and 2-chloro-butadiene, and copolymers of these compounds with acrylonitrile, methyl methaacrylate, styrene, and isobutylene.ALSO:a ,b  - bis - (2 - hydroxy - 5 - methylphenyl)-ethane in which there is in the 3 position of each of the two phenyl radicals a substituent with not more than 8 carbon atoms chosen from the group consisting of alkyl, cycloalkyl and alkylcycloalkyl may be used in the preservation of natural and synthetic rubber as described in Groups IV (a) and V.  Specified compounds are: 1 : 2 - bis - (2 - hydroxy - 3,5 - dimethylphenyl) ethane, 1 : 2 - bis - (2 - hydroxy - 3 - tert - butyl-5 - methylphenyl) ethane, 1 : 2 - bis - (2-hydroxy - 3 - tert - amyl - 5 - methylphenyl) ethane, 1 : 2 - bis - (2 - hydroxy - 3 - a  - methylcyclohexyl - 5 - methylphenyl) ethane, 1 : 2-bis - (2 - hydroxy - 3 - n - butyl - 5 - methylphenyl) ethane, 1 : 2 - bis - (2 - hydroxy - 3-cyclohexyl - 5 - methylphenyl) ethane.  In a typical method of preparation p-cresol is reacted with gaseous isobutylene in the presence of sulphuric acid and then subsequently neutralized to produce 4-methyl-6-tert.-butylphenol which is then reacted with paraform and hydrogen chloride in ether to form 2-hydroxy-3-tert.-butyl-5-methylbenzyl chloride which on treatment with sodium bicarbonate gives 2-tert. - butyl - 4 - methyl - 6 - methylenecyclohexadien-1-one which is then reduced by zinc and hydrochloric acid to produce 1 : 2-bis-(2 - hydroxy - 3 - tert. - butyl - 5 - methylphenyl) ethane.ALSO:Natural rubber is preserved by incorporating an a  b  - bis - (2 - hydroxy - 5 - methylphenyl) - ethane in which there is in the 3 - position of each of the two phenyl radicals a substituent with not more than 8 carbon atoms chosen from the group consisting of alkyl, cycloalkyl, and alkylcyclo alkyl.  The preferred substituted ethanes are 1 : 2 bis (2 - hydroxy - 3 tert butyl - 5 - methylphenyl) ethane, 1 : 2 bis (2 - hydroxy - 3 tert amyl - 5 - methyl phenyl) ethane, and 1 : 2 bis (2 - hydroxy - 3 - a  - methyl cyclohexyl - 5 - methyl phenyl) ethane and these may be made according to the methods described in Group IV(b); from 0.25 to 2.0 per cent based on the weight of the rubber is normally used.  In typical mixes, one of the above specified substituted ethanes is added to a mix comprising pale crepe rubber, zinc oxide, blanc fixe, stearic acid, and sulphur and to which may be added titanium dioxide, zinc diethyl dithiocarbomate or tetramethyl thiuram monosulphide.  In addition 1 : 1 bis (2 hydroxy, 3 - 5 - dimethyl phenyl) ethane, 1 : 2 bis (2 hydroxy 3n. butyl 5 methyl phenyl) ethane, 1 : 2 bis (2 hydroxy 3 sec. butyl 5 methyl phenyl) ethane, and 1 : 2 bis (2 hydroxy 3 cyclohexyl 5 methyl phenyl) ethane, are specified.