Patent GB-788794-A (GB)
Title: New composite antioxidants comprising bis-(hydroxy-dimethylphenyl) derivatives of butane and methane
Inventor: PALFREEMAN HERBERT
IPC: C07C39/16
Filed: 1954-12-03
Abstract: A process for the manufacture of antioxidants comprises treating 0.8-1.3 molecular proportions of n-butyraldehyde in the presence of an acid condensing agent, e.g. hydrochloric or sulphuric acid, with 2 molecular proportions of a mixture consisting of 2 : 4- and 2 : 5-dimethyl phenols, with one-half to one-quarter its weight consisting of 2 : 5-dimethylphenol and if desired up to one-eighth its weight consisting of coal-tar distillation products boiling at about the same temperatures as the 2 : 4- and 2 : 5-dimethylphenols, and then before isolating the antioxidant treating with 0.1-0.4 molecular proportions of formaldehyde and the invention further comprises composite antioxidants obtainable by the above process containing bis - (2 - hydroxy - 3 : 5 - dimethylphenyl) butane, bis - (4 - hydroxy - 2 : 5 - dimethylphenyl) butane, 2 : 41-dihydroxy-3 : 5 : 21 : 51 tetramethyldiphenylbutane and bis-(4-hydroxy-2 : 5-dimethylphenyl) methane.  The products are employed as antioxidants in natural or synthetic rubber compositions (see Groups IV (a) and V).  Examples are furnished.  Specifications 525,737, [Group IV], and 621,004 are referred to.ALSO:Antioxidants for synthetic rubbers are obtained by treating 0.8-1.3 molecular proportions of n-butyraldehyde in the presence of an acid condensing agent with 2 molecular proportions of a mixture consisting of 2 : 4- and 2 : 5-dimethyl phenols, with one half to one quarter its weight consisting of 2 : 5-dimethylphenol and if desired up to one eighth its weight consisting of tar distillation products boiling at about the same temperatures as the 2 : 4- and 2 : 5-dimethylphenols and then before isolating the antioxidant treating with 0.1-0.5 molecular proportions of formaldehyde.  Synthetic rubbers mentioned include polymers of butadiene-1 : 3, isobutene and 2-chlorobutadiene1 : 3 and copolymers of these compounds with acrylonitrile, styrene and methyl methacrylate.  The antioxidants may be incorporated with the rubber or rubber latex and conventional ingredients and the mixtures may be cured by treatment with sulphur monochloride or heating.  In Example (2) a mixture of Neoprene GN, magnesium oxide, stearic acid, china clay, whiting, petroleum jelly, cumar resin, titanium dioxide, zinc oxide and an antioxidant prepared in accordance with the invention is cured by heating.  Specifications 525,737 and 621,004, [both in Group V], are referred to.ALSO:Antioxidants for natural rubber are obtained by treating 0,8-1,3 molecular proportions of n-butyraldehyde in the presence of an acid condensing agent with 2 molecular proportions of a mixture consisting of 2 : 4- and 2 : 5-dimethylolphenols, with one half to one quarter of its weight consisting of 2 : 5-dimethylolphenol and if desired up to one eighth its weight consisting of coal-tar distillation products boiling at about the same temperatures as the 2 : 4- and 2 : 5-dimethylphenols, and then before isolating the antioxidants treating with 0,1-0,4 molecular proportions of formaldehyde.  The antioxidants may be mixed with the rubber or rubber latex with other conventional ingredients and the mixes cured by heat-treatment or by treatment in the cold with sulphur monochloride.  In examples, a mixture of pale crepe natural rubber, zinc oxide, blanc fixe, stearic acid, sulphur, diphenyl guanidine and an antioxidant prepared in accordance with the invention is vulcanized by heating; in a similar process zinc diethylcarbamate and titanium di-oxide are employed in the composition instead of the diphenyl guanidine (1); and a mixture of natural rubber latex, aqueous cetyl alcohol-ethylene oxide condensation product, aqueous dispersions of sulphur, zinc oxide, zinc diethyl dithiocarbamate, and the antioxidant is cured by heating.  Specifications 525,737 and 621,004 are referred to.