Patent GB-900116-A (GB)
Title: A process for the preparation of bis (hydroxyphenyl) methanes
Inventor: ROCKLIN ALBERT L
IPC: B01J27/24
Filed: 1960-11-21
Abstract: An organic material subject to oxidative deterioration contains as stabilizer 0,0001 to 10% by weight of a bis (hydroxyphenyl) poly (oxymethylene) ether of the formula <FORM:0900116/III/1> in which two of the groups R bound to different rings are hydroxyl groups and each of the other groups R are hydrogen atoms or alkyl groups and n is an integer of at least 1.  Organic materials mentioned include gasoline lubricating oils, edible oils such as vegetable oil, fish oil, olive oil or corn oil and animal and vegetable fats including lard and hydrogenated vegetable oils. In examples bis (3,5-di-tert. butyl-4-hydroxy-benzyloxy) methane and related polyoxymethylene derivatives are added in a concentration of 10 mg/dl to a commercial gasoline. Specification 806,961 is referred to.ALSO:A natural or synthetic rubber or a polyolefin contains as antioxidant 0,0001 to 10% by weight of a bis(hydroxyphenyl) poly(oxymethylene ether) of the formula <FORM:0900116/IV(a)/1> in which two of the groups R bound to different rings are hydroxyl groups and each of the other groups R are hydrogen atoms or alkyl groups and n is an integer of at least 1. The polyethers may be incorporated in polybutadiene, polyisoprene and butadiene/styrene rubbers and polyethylene, polypropylene and their copolymers. Specification 806,961 is referred to.ALSO:The invention comprises bis(hydroxyphenyl) poly(oxymethylene) ethers of the formula <FORM:0900116/IV (b)/1> in which two of the groups R bound to different rings are hydroxyl groups and each of the other groups R are hydrogen or the same or different alkyl groups and n is a positive integer having a value of at least 1; and a process for their preparation by (a) reacting a phenol with formaldehyde in the presence of a secondary or tertiary monohydric alkanol and a catalytic amount of a base at a temperature below 50 DEG C. or by (b) reacting a hydroxy benzyl alcohol with formaldehyde in the presence of a secondary or tertiary monohydric alkanol and a catalytic amount of a base. The phenol used is preferably a 2,4- or 2,6-dialkyl phenol where the alkyl groups contain up to 8 carbon atoms and one at least is secondary or tertiary.  The reaction is preferably carried out at 0-25 DEG C. under anhydrous conditions using an inorganic base such as sodium hydroxide and an alcohol which is liquid at below 25 DEG C. and which contains 3-8 carbon atoms.  The mixture of products obtained may be separated into the component ethers using a molecular still.  Examples describe the reaction of 2,6-di-t.butyl-, 2-t.butyl-6-methyl-, 2,6-di-isopropyl and 2-phenyl-6-methyl phenol with formaldehyde.  Bis-hydroxyphenyl methanes are prepared by subjecting a bis - hydroxyphenyl - poly (oxymethylene) ether of the above formula to a temperature above 15 DEG C. in the presence of a monohydric secondary or tertiary alkanol and a catalytic amount of a base. The reaction takes place preferably under anhydrous conditions at a temperature of 50-100 DEG C. in the presence of an inorganic base such as sodium hydroxide and an alkanol which is liquid at 15 DEG C., boils at above 100 DEG C. and contains 3-8 carbon atoms.  A phenol or alkyl phenol, preferably substituted similarly to the phenyl ring in the polyether reactant, may also be added to the reaction mixture.  Examples describe the preparation of bis(3,5-di-t.butyl- and di-isopropyl-4-hydroxyphenyl) methane.  The hydroxyphenyl polyethers may be used as antioxidants for organic materials subject to oxidative deterioration, e.g. methyl linoleate, and may be hydrogenated to give substituted or unsubstituted p-cresols and hydrolysed to give substituted or unsubstituted p-hydroxy benzyl alcohols.  The hydroxyphenyl polyethers containing unhindered o- or p-hydroxy groups may be reacted with epihalohydrins under basic conditions to give epoxy resins.  Specification 806,961 is referred to.ALSO:Animal and poultry feed such as silage and chicken feed, also butter and other dairy produce, may be stabilized against oxidation by the incorporation of a bis (hydroxyphenyl) poly (oxymethylene) ether of the formula <FORM:0900116/I/1> in which two of the groups R bound to different rings are hydroxyl groups, each of the other groups R is hydrogen atom or an alkyl group and n is an integer of at least 1.  Specification 806,961 is referred to.ALSO:Foodstuffs such as fish, meat, butter, and other dairy produce may be stabilized against oxidation by the incorporation of a bis-(hydroxyphenyl) poly-(oxymethylene) ether of the formula <FORM:0900116/VI/1> in which two of the groups R bound to different rings are hydroxyl groups, each of the other groups R is a hydrogen atom or an alkyl group and n is an integer of at least 1.  In an example, a 3,5-di-tert. butyl-4-hydroxybenzyl ether of the general formula in which n = 8 is sprayed in a dioxan solution on to sliced bacon and the development of a rancid odour is delayed.  The ether may be impregnated in paper used for food packaging.  Specification 806,961 is referred to.