Patent GB-806961-A (GB)
Title: Alkylated bis-phenols and hydroxy benzylamines and their method of manufacture
IPC: C08K5/13
Filed: 1956-09-18
Abstract: The invention comprises the use as antioxidants of compounds of general formula <FORM:0806961/III/1> where X is <FORM:0806961/III/2> or <FORM:0806961/III/3> R1 and R2 are C3-C8 alkyl, branched on the alpha atom, R3 is C1-C4 alkyl or <FORM:0806961/III/4> and R4 is hydrogen or C1-C4 alkyl.  Compounds specified are 1,1-bis-(3,5-di-tert.-butyl-4-hydroxyphenyl) - methane; 1,1 - bis - (3,5 - diisopropyl - 4 - hydroxyphenyl) - methane; 1,1 - bis - (3 - isopropyl - 5 - tert - butyl - 4 - hydroxyphenyl) - methane; 1,1 - bis - (3,5 - di - (1,1,3,3-tetramethyl-butyl) - 4 - hydroxyphenyl) - methane; 1,1 - bis - (3 - sec. - butyl - 5 - tert. - butyl - 4-hydroxyphenyl methane; N,N - dimethyl - N - (3,5 - diisopropyl - 4 - hydroxybenzyl)-amine; N,N - dimethyl - N - (3,5 - di - tert. - butyl - 4 - hydroxybenzyl) - amine; N1-methyl-N,N1 - bis - (3,5 - di - tert. - butyl - 4 - hydroxybenzyl) - amine; N,N - di - butyl - N - (3,5 - di-tert - butyl - 4 - hydroxybenzyl) - amine and N - tert. - butyl - N - (3,5 - di - tert. - butyl - 4 - hydroxybenzyl) - amine. The compounds may be incorporated in hydrocarbon lubricating oils, steam turbine oils, grease, paraffin wax, linseed oil, cod liver oil, coconut oil, corn oil, lard; gasolines containing lead alkyl anti-knock agents, such as tetraethyl lead; diesel fuels, domestic heating oils, and bunker and residual fuel oils.  Suitable amounts of the antioxidant are from about 0.001 to about 3 per cent by weight of the material to be protected.ALSO:The invention comprises the use as antioxidants of compounds of general formula <FORM:0806961/IV (a)/1> where X is <FORM:0806961/IV (a)/2> or <FORM:0806961/IV (a)/3> R1 and R2 are C3-C8 alkyl, branched on the alpha atom, R3 is C1-C4 alkyl or <FORM:0806961/IV (a)/4> and R4 is hydrogen or C1-C4 alkyl.  Compounds specified are 1,1-bis-(3,5-di-tert.-butyl-4-hydroxyphenyl) methane; 1,1-bis-(3,5-diisopropyl - 4 - hydroxyphenyl) - methane; 1,1 - bis - (3 - isopropyl - 5 - tert. - butyl - 4 - hydroxyphenyl) - methane; 1,1 - bis - (3,5 - di - (1,1,3,3-tetramethylbutyl) - 4 - hydroxyphenyl) - methane; 1,1 - bis - (3 - sec. - butyl - 5 - tert. - butyl - 4 - hydroxyphenyl) - methane; N,N - dimethyl-N - (3,5 - diisopropyl - 4 - hydroxybenzyl) - amine; N,N - dimethyl - N - (3,5 - di - tert. - butyl - 4 - hydroxybenzyl) - amine; N - methyl - N,N - bis - (3,5 - di - tert. - butyl - 4 - hydroxybenzyl) - amine; N,N - di - butyl - N - (3,5 - di - tert. - butyl - 4 - hydroxybenzyl) - amine and N - tert. - butyl - N - (3,5 - di - tert. - butyl - 4 - hydroxybenzyl)-amine.  The compounds may be incorporated in, e.g., natural rubber, polyethylene, polystyrene, and isobutylene-styrene copolymers.  Suitable amounts are from about 0.001 to about 3 per cent by weight of the material to be protected.ALSO:The invention comprises compounds of the general formula <FORM:0806961/IV (b)/1> where X is (1) <FORM:0806961/IV (b)/2> or (2) <FORM:0806961/IV (b)/3> R1 and R2 are C3-C8 alkyl groups and are branched on their alpha carbon atoms, R3 is C1-C4 alkyl or <FORM:0806961/IV (b)/4> and R4 is hydrogen or C1-C4 alkyl.  The 1,1-bis - (3,5 - dialkyl - 4 - hydroxy phenyl) methanes are prepared by reacting preferably one mol. of formaldehyde with approximately two mols. of a 2,6-dialkyl phenol, in which both alkyl groups contain 3 to 8 carbon atoms, both of said alkyl groups being branched on their alpha carbon atoms, using an alkali metal hydroxide, such as sodium hydroxide as a catalyst.  The condensation may be conducted in a solvent consisting of a monohydric alcohol containing 1-8 carbon atoms, preferably isopropyl alcohol, at temperatures between about 20 DEG  to about 100 DEG  C.  The catalyst is present in about 0.5 to about 3 per cent by weight of the dialkyl phenol used.  The 3,5-dialkyl - 4 - hydroxybenzyl amines are prepared by reacting a 2,6-dialkyl phenol as defined, formaldehyde, and a primary or secondary amine in which each alkyl group contains from 1 to 4 carbon atoms, in a solvent, preferably a monohydric alcohol containing 1-6 carbon atoms, at a temperature 20-100 DEG  C.  When preparing the N,N-dialkyl-N - (3,5 - dialkyl - 4 - hydroxy benzyl) - amines, one mol. of formaldehyde and one mol. of a secondary amine are employed per mol. of appropriate 2,6-dialkyl phenol.  In the case of N - alkyl - N,N - bis - (3,5 - dialkyl - 4 - hydroxybenzyl)-amines, one mol. of formaldehyde and one half of a mol. of primary amine are used per mol. of dialkyl phenol.  When preparing compounds which contain one hydrogen atom and one alkyl group on the nitrogen atom, one mol. of formaldehyde and a large excess of primary amine (about 8 to 10 mols. per mol. of dialkyl phenol) are used in the presence of an excess of a monohydric alcohol solvent.  Examples are given of the preparation of 1,1-bis-(3,5-ditert.-butyl-4-hydroxyphenyl)-methane, 1,1-bis-(3,5-di - isopropyl - 4 - hydroxyphenyl) - methane, N,N - dimethyl - N - (3,5 - diisopropyl - 4 - hydroxybenzyl) - amine, N,N - dimethyl - N - (3,5 - di - tert. - butyl - 4 - hydroxy - benzyl) - amine, N - methyl - N,N - bis - (3,5 - di - tert. - butyl - 4 - hydroxybenzyl) - amine. Other compounds mentioned are 1,1-bis-(3-isopropyl-5-tert. - butyl - 4 - hydroxyphenyl) - methane, 1,1 - bis - (3,5 - di - (1,1,3,3 - tetramethylbutyl) - 4 - hydroxyphenyl) - methane, and 1,1 - bis - (3 - sec. - buty. - 5 - tert. - butyl - 4 - hydroxyphenyl)-methane.ALSO:Oxidation of edible oils and fats, e.g. linseed, cod liver, coconut and corn oils, butter and lard, is retarded by incorporation of compounds of the general formula <FORM:0806961/VI/1> where X is <FORM:0806961/VI/2> R1 and R2 are C3-C8 alkyl branched on the alpha atom, R3 is C1-C4 alkyl or <FORM:0806961/VI/3> and R4 is hydrogen or C1-C4 alkyl.  Compounds specified are 1,1-bis-(3,5-di-tert-butyl-4-hydroxy-phenyl) methane; 1,1 - bis - (3,5 - di - isopropyl-4 - hydroxyphenyl) methane; 1,1 - bis - (3 - isopropyl - 5 - tert - butyl - 4 - hydroxyphenyl) methane; 1,1 - bis - (3,5 - di - (1,1,3,3 - tetramethylbutyl) - 4 - hydroxyphenyl) methane; 1,1 - bis - (3 - sec. - butyl - 5 - tert - butyl - 4 - hyphoxyphenyl) methane; N1,N1 - dimethyl-N - (3,5 - diisopropyl - 4 - hydroxybenzyl) amine; N,N - dimethyl - N - (3,5 - di - tertbutyl - 4 - hydroxybenzyl) amine; N1 - methylN1,N1 - bis - (3,5 - di - tert - butyl - 4 - hydroxybenzyl) amine; N1,N1-dibutyl-N-(3,5-di-tertbutyl-4-hydroxybenzyl) amine and N-tert-butylN - (3,5 - di - tert - butyl - 4 - hydroxybenzyl) amine. Suitable amounts are from 0.001 to 3 per cent by weight of the material to be protected.