Patent GB-693851-A (GB)
Title: Improvements in or relating to stabilizing solid organic materials
IPC: C08K5/00
Filed: 1950-12-29
Abstract: Solid organic materials are stabilized by adding a small proportion of an acyl-p-aminophenol having the general formula <FORM:0693851/IV (a)/1> wherein R represents a hydrocarbon radical containing from 1-24 carbon atoms and R1 and R11 represent hydrogen or alkyl substituent radicals containing from 1 to 20 and preferably from 4-15 carbon atoms.  The acyl-p-aminophenols may be made according to the methods described in Group IV (b).  The acyl group may be derived from one of the following acids: acetic, butyric, caprylic, capric, lauric, myristic, palmitic, stearic, undecylenic, oleic, linoleic, cyclohexylvaleric, cyclohexyl, caproic, C8 oxo acids, C9 oxo acids and naphthenic acids.  Specified compounds which may be used are N-lauroyl-p-aminophenol, N-acetyl-p-amino-3-pentadecyl phenol, N - n - valeroyl - 4 - amino - 3-pentadecyl phenol, N-n-pentanoyl-4-amino-3-pentadecyl phenol, N-n-propanoyl-4-amino-3-pentadecyl phenol, N - n - pentanoyl - 4 - amino-2,6-ditertiary butyl phenol, N-n-hexyl-4-amino-2-hexyl phenol. The organic substances which may be stabilized according to the invention are synthetic rubbers such as GR-I, polymers of 1,3-butadiene, isoprene, 2,3-dimethylbutadiene - 1,3, 2 - chlorobutadiene, piperylene, 2-methylpentadiene-1,3, and copolymers of butadiene-1,3 with acrylonitrilemethyl methacrylate, styrene, alpha-methyl styrene, vinyl naphthalene, vinyl ketones, vinylidene chloride, methyl methacrylate and dimethyl fumarate; resins such as polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, copolymers of vinyl chloride with vinyl acetate or vinylidene chlorides, polyvinyl butyral, or nitrocellulose, or ethyl cellulose which may be plasticized with the branched alcohol esters of phthalic acid, sebacic acid, oleic acid, stearic acid, lauric acid, or maleic acid. The acyl-p-amino phenols are preferably added in a proportion of 0.25-2.0 per cent, and may be used in conjunction with other anti-oxidants such as phenyl-naphthylamine, naphthols, substituted phenols, such as 2,6 - ditertiary - butyl - 4 - methyl phenol, substituted catechols, substituted hydroquinones, alkyl phenol sulphides and ketone-amine condensation products.ALSO:Solid organic materials are stabilized by adding a small proportion of an acyl-p-aminophenol having the general formula <FORM:0693851/IV (b)/1> wherein R represents a hydrocarbon radical containing from 1-24 carbon atoms and R1 and R11 represent hydrogen or alkyl substituent radicals containing from 1 to 20 and preferably from 4-15 carbon atoms.  The acyl-p-aminophenols may be made by reacting an approximately equimolar amount of an acid anhydride or anhydrous acid in the presence of a water entraining solvent such as benzene, toluene or xylene with an aminophenol.  The solid product is then dehydrated by evaporation and the product washed with water or dilute sodium carbonate solution.  The acyl group may be derived from one of the following acids: acetic, butyric, caprylic, capric, lauric, myristic, palmitic, stearic, undecylenic, oleic, linoleic, benzoic, cyclohexylvaleric, cyclohexyl caproic, C8 oxo acids, C9 oxo acids and naphthenic acids.  Specified compounds which may be used are N-lauroyl-p-aminophenol, N-acetyl-p-amino-3-pentadecyl phenol, N - n - valeroyl - 4 - amino - 3 - pentadecyl phenol, N - n - pentanoyl - 4 - amino - 3 - pentadecyl phenol, N - n - propanoyl - 4 - amino - 3 - pentadecyl phenol, N - n - pentanoyl - 4 - amino - 2,6 - ditertiary butyl phenol, N - n - hexyl - 4 - amino - 2 - hexyl phenol.  The organic substances which may be stabilized according to the invention are lubricating greases, waxes, natural rubber, synthetic rubbers such as GR-I, polymers of 1,3-butadiene, isoprene, 2,3-dimethyl butadiene-1,3, 2-chlorobutadiene, piperylene, 2-methyl-pentadiene-1,3, and copolymers of butadiene-1,3-acrylonitrile, methyl methacrylate, styrene, alpha methyl styrene, vinyl naphthalene, vinyl ketones, vinylidene chloride, methyl methacrylate and dimethyl fumarate; resins such as polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, copolymers of vinyl chloride with vinyl acetate or vinylidene chlorides, polyvinyl butyral, or nitrocellulose, or ethyl cellulose which may be plasticized with the branched alcohol esters of phthalic acid, sebacic acid, oleic acid, stearic acid, lauric acid or maleic acid. The greases may be obtained by dispersing any of the grease-making soaps in a lubricating oil, e.g. calcium, strontium, barium, potassium, sodium or lithium with hydrogenated fish oil acids, stearic acid, hydroxy stearic acid, oleic acid, palmitic acid, lauric acid, tallow or coconut oil. The oil base in which the soaps may be dispersed are the natural or synthetic mineral oil distillates or long-chain esters of aliphatic acids, esters of sebacates and adipates, polymerized p  cracked wax, acylated aromatics, polyglycol esters, polyglycol ethers and polyglycol ether esters.  The acyl p-amino phenols are preferably added in a proportion of 0.25-2.0 per cent, and may be used in conjunction with other antioxidants such as phenyl-naphthylamine, naphthols, substituted phenols, such as 2,6 - ditertiary - butyl - 4 - methyl phenol, substituted catechols, substituted hydroquinones, alkyl phenol sulphides and ketoneamine condensation products.ALSO:Lubricating greases and waxes are stabilized by adding a small proportion of an acyl-p-aminophenol having the general formula <FORM:0693851/III/1> wherein R represents a hydrocarbon radical containing from 1-24 carbon atoms and R1 and R11 represent hydrogen or alkyl substituent radicals containing from 1 to 20 and preferably from 4-15 carbon atoms.  The acyl-p-aminophenols may be made according to the methods described in Group IV(b).  The acyl group may be derived from one of the following acids:-acetic, butyric, caprylic, capric, lauric, myristic, palmitic, stearic, undecylenic, oleic, linoleic, benzoic, cyclohexylvaleric, cyclohexyl caproic, C8 oxo acids, C9 oxo acids and naphthenic acids. Specified compounds which may be used are N-lauroyl p-aminophenol, N-acetyl-p-amino-3 pentadecyl phenol, N-n-valeroyl-4-amino-3 pentadecyl phenol, N-n-pentanoyl- 4-amino-3 pentadecyl phenol, N-n-propanoyl-4-amino-3 pentadecyl phenol, N-n-pentancyl-4-amino-2, 6 ditertiary butyl phenol, N-n-hexyl-4-amino-2 hexyl phenol.  The greases may be obtained by dispersing any of the grease-making soaps in a lubricating oil, e.g. calcium, strontium, barium, potassium, sodium or lithium with hydrogenated fish oil acids, stearic acid, hydroxy stearic acid, oleic acid, palmitic acid, lauric acid, tallow or cocoanut oil.  The oil base in which the soaps may be dispersed are natural synthetic, such as mineral oil distillates or long chain esters of aliphatic acids, esters of sebacates and adipates, polymerized cracked wax, acylated aromatics, polyglycol ether esters. The acyl-p-amino phenols are preferably added in a proportion of 0.25-2.0 per cent, and may be used in conjunction with other anti-oxidants such as phenyl-naphthylamine naphthols, substituted phenols, such as 2, 6 ditertiary-butyl-4-methyl phenol, substituted catechols,substituted hydroquinones, alkyl phenol sulphides and ketone-amine condensation products.ALSO:Natural rubber is stabilized by adding a small proportion of an acyl-p-aminophenol having the general formula <FORM:0693851/V/1> wherein R represents a hydrocarbon radical containing from 1-24 carbon atoms and R1 and R11 represent hydrogen or alkyl substituent radicals containing from 1 to 20 and preferably from 4-15 carbon atoms.  The acyl-p-aminophenols may be made according to the methods described in Group IV (b).  The acyl group may be derived from one of the following acids:-acetic, butyric, caprylic, capric, lauric, myristic, palmitic, stearic, undecylenic, oleic, linoleic, benzoic, cyclohexylvaleric, cyclohexyl, caproic, c8 oxo acids, c9 oxo acids and naphthenic acids.  Specified compounds which may be used are N-lauroyl p-aminophenol, N-acetyl-p-amino-3 pentadecyl phenol, N-n-valeroyl-4-amino-3 pentadecyl phenol, N-n-pentanoyl-4-amino 3 pentadecyl phenol, N-n-propanoyl-4-amino-3 pentadecyl phenol, N-n-pentanoyl-4-amino-2, 6 ditertiary butyl phenol, N-n-hexyl-4-amino-2 hexyl phenol.  The acyl-p-amino phenols are preferably added in a proportion of 0.25-2.0 per cent., and may be used in conjunction with other anti-oxidants such as phenyl-naphthylamine, naphthols, substituted phenols, such as 2, 6, ditertiary-butyl-4-methyl phenol, substituted catechols, substituted hydroquinones, alkyl phenol sulphides and ketoneamine condensation products.