Patent GB-779360-A (GB)
Title: Improvements in or relating to stabilizers for organic compositions
IPC: C09K15/14
Filed: 1954-08-05
Abstract: A composition comprising an organic material susceptible to deterioration by oxidation, which deterioration can be arrested by the addition of an antioxidant includes as an antioxidant a hydroxyaromatic amide of the formula: <FORM:0779360/IV(a)/1> or <FORM:0779360/IV(a)/2> or <FORM:0779360/IV(a)/3> or a phenolate of such an amide with an alkali metal or alkaline-earth metal, R being an aliphatic, alicyclic, aromatic or alkaryl group and R1 and R11 being alkyl groups. The organic materials specified include resins and synthetic rubbers, e.g. polymers of isobutylene, ethylene, 1,3-butadiene, isoprene, 2-chlorobutadiene, piperylene and cyclopentadiene, and copolymers thereof with methacrylonitrile, styrene, vinyl naphthalenes, vinyl ketones and vinylidene chloride and diethyl fumarate.  The amide may be incorporated in a synthetic rubber composition as a solid by milling, or in solution or suspension, or may be added to a synthetic rubber latex.  The amide may also be used in combination with other antioxidants, e.g. naphthols, hydroquinones, alkyl phenol sulphides and acyl p-aminophenols.ALSO:A composition comprising an organic material susceptible to deterioration by oxidation, which deterioration can be arrested by the addition of an antioxidant includes as an antioxidant a hydroxyaromatic amide of the formula: <FORM:0779360/IV(b)/1> or a phenolate of such an amide with an alkali metal or alkaline-earth metal, R being an aliphatic, alicyclic, aromatic or alkaryl group and R1 and R11 being alkyl groups. The proportion of amide is preferably 0.01 to 5 per cent by weight of the organic material to be stabilized.  The organic materials are not intended for human consumption and include natural rubber, resins, e.g. vinyl resin, synthetic rubbers, e.g. polymers of 1,3-butadiene, isoprene, 2-chlorobutadiene, piperylene and cyclopentadiene, and copolymers thereof with methacrylonitrile, styrene, vinyl naphthalenes, vinyl ketones, vinylidene chloride and diethyl fumarate, insecticides, soaps, waxes, hormones, vitamins, fats, oils, greases and esters of phthalic, sebacic, oleic, stearic, lauric and maleic acids.  The amide may also be used in combination with other antioxidants, e.g. naphthols, hydroquinones, alkyl phenol sulphides and acyl p-aminophenols. Preferred arylamides are of formula: <FORM:0779360/IV(b)/2> where R has at least 2 C atoms and R1 is an alkyl group, e.g. methyl, isopropyl, tert.-butyl, octyl or decyl, and their phenolates with alkali metals, e.g. sodium and lithium, and alkaline earth metals.  Hydroxybenzamides are preferred in which R has from 4-16 C atoms.  The benzamides are preferred in which R has from 4-16 C atoms.  The benzamides, some of which are stated to be novel are made by reacting appropriate benzoic acids and amines in equimolar quantities at elevated temperatures, e.g. 150 DEG  C. or higher, optionally in the presence of catalysts such as boric acid and water entrainers.  Examples show the preparation of N-(n-butyl)-(decyl) - and (hexadecyl) - p - hydroxybenz-amides and their use as antioxidants in rubber, synthetic rubber, polymers and mineral greases.  Other specified compounds are N-lauryl-dodecyl-, octadecyl- and isododecyl-p-hydroxybenzamides, N - isodecyl - p - hydroxy - m-tert. - butylbenzamide and N - dodecyl - p-hydroxy-m-propylbenzamide.ALSO:A composition comprising an organic material susceptible to deterioration by oxidation, which deterioration can be arrested by the addition of an antioxidant, includes as an antioxidant a hydroxyaromatic amide of the formula <FORM:0779360/III/1> or <FORM:0779360/III/2> or <FORM:0779360/III/3> or a phenolate of such an amide with an alkali metal or alkaline-earth metal, R being an aliphatic, alicyclic, aromatic or alkaryl group and R1 and R11 being alkyl groups. The proportion of amide is preferably 0.01 to 5 per cent by weight of the organic material to be stabilized.  The organic materials specified include soaps, waxes, fats, oils and greases. The amide may be used alone or in combination with other antioxidants, e.g. naphthols, hydroquinones, alkyl phenol sulphides and acyl p-aminophenols.  In the preparation of a grease compound, there may be formed in situ by the reaction of an amine and p-hydroxybenzoic acid an amide such as N-lauryl - p - hydroxybenzamide, N - dodecyl - p - hydroxybenzamide, N - octadecyl - p - hydroxybenzamide, N - isododecyl - p - hydroxybenzamide, N - isododecyl - p - hydroxy - m tert - butylbenzamide, and N - dodecyl - p - hydroxy - m-propylbenzamide. The grease composition may be prepared by dispersing in a lubricating oil a soap of an alkaline-earth or alkali metal with hydrogenated fish oil acids, stearic, hydroxystearic, oleic, palmitic, or lauric acid, tallow, coconut oil, or saturated or unsaturated glycerides of fatty acids, or mixtures thereof.  The lubricating oil may be selected from mineral oil distillates, or long-chain esters of aliphatic acids, esters of dibasic acids such as sebacates and adipates, polymerized cracked wax, acylated aromatic compounds and polyglycol esters, ethers and ether esters.  In examples, a grease composition is prepared by heating a mixture (in parts by weight) of rapeseed oil 29, sodium hydroxide 5.92, petroleum sulphonate 1, lubricating oil 63.08 and 1 part of (1) N - hexadecyl - p - hydroxybenzamide, (2) N-lauryl - p - hydroxy - benzamide, and (3) N - dodecyl - p - hydroxybenzamide, respectively.ALSO:A composition comprising an organic material susceptible to deterioration by oxidation, which deterioration can be arrested by the addition of an antioxidant includes as an antioxidant a hydroxymatic amide of the formula:  <FORM:0779360/V/1> or a phenolate of such an amide with an alkali metal or alkaline-earth metal, R being an aliphatic, alicyclic, aromatic or alkaryl group, and R1 and R11 being alkyl groups.  The proportion of amide is preferably 0,01 to 5 per cent by weight of the organic material to be stabilized.  The organic materials are not intended for human consumption and include natural rubber, resins, e.g. vinyl resin, synthetic rubbers, e.g. polymers of 1, 3 butadiene, isoprene, 2-chlorobutadiene, piperylene, and cyclopentadiene, and copolymers thereof with methacrylonitrile, styrene, vinyl naphthalenes, vinyl ketones, vinylidene chloride, and diethyl fumarate, insecticides, soaps, waxes, hormones, vitamins, fats, oils, greases, and esters of phthalic, sebacic, oleic, stearic, lauric, and maleic acids.  The amide may be incorporated in a synthetic rubber composition by milling or may be added to a synthetic rubber latex.  The amide may also be used in combination with other antioxidants, e.g. naphthols, hydroquinones, alkyl phenol sulphides, and acyl p-aminophenols. In the preparation of a grease compound there may be formed in situ by the reaction of an amine and p-hydroxybenzoic acid an amide such as N-lauryl-p-hydroxybenzamide, N-dodecyl-p-hydroxybenzamide, N-octadecyl-p-hydroxybenzamide, N-isododecyl-p-hydroxybenzamide, N-isododecyl-p-hydroxy-m-tert.-butylbenzamide, and N-dodecyl-p-hydroxy-m-propylbenzamide.  The grease composition may be prepared by dispersing in a lubricating oil a soap of an alkaline earth or alkali metal with hydrogenated fish oil acids, stearic, hydroxy stearic, oleic, palmitic, or lauric acids, tallow, coconut oil, or saturated or unsaturated glycerides of fatty acids, or mixtures thereof.  The lubricating oil may be selected from mineral oil distillates, or long chain esters of aliphatic acids, esters of dibasic acids such as sebacates and adipates, polymerized cracked wax, acylated aromatic compounds, and polyglycol esters, ethers, and ether esters.  In examples a grease composition is prepared by heating a mixture (in parts by weight) of rapeseed oil 29, sodium hydroxide 5,92, petroleum sulphonate 1, lubricating oil 63,08, and 1 part of (1) N-hexadecyl-p-hydroxybenzamide, (2) N-layryl-p-hydroxybenzamide, and (3) N-dodecyl-p-hydroxybenzamide, respectively.ALSO:Organic materials not intended for human consumption and susceptible to deterioration by oxidation, exemplified by reins, insecticides, soaps, waxes, hormones, vitamins, rubbers, fats, oils and greases, are preserved by addition of hydroxyaromatic amides of the formula <FORM:0779360/VI/1> or a phenolate of such an amide formed by replacing the hyrogen of the hydroxyl group by alkali metal or alkaline earth metal, R being an aliphatic, alicyclic, aromatic or alkaryl group, and R1 and R11 being alkyl groups.  A representative member of the class of compounds is N - (n - butyl) p - hydroxybenzamide.  The compounds may be used in conjunction with other antioxidants such as naphthols, hydroquinones, alkyl phenol sulphides and acyl p - aminophenols.