Patent GB-605848-A (GB)
Title: Improvements in or relating to the manufacture of long chain carboxylic acids
IPC: C08K5/09
Filed: 1946-03-18
Abstract: Carboxylic acids containing a long chain of -CH2- groups are obtained by the action of ethylene on carboxylic acids which are free from olefinic or acetylenic unsaturation and have at least one a -hydrogen atom, the reaction being effected at a raised temperature and pressure in the presence of a catalyst capable of converting ethylene under these conditions into a solid polymer.  The effect of the reaction is to convert an acid RCOOH into an acid R(CH2)nCOOH, where n may be 6-50 or more.  Specified acids which may be treated are acetic, propionic, butyric, valeric and homologous acids, e.g. octanoic, decanoic, lauric or myristic acid, isobutyric acid, butane-2-carboxylic acid, pentane-3-carboxylic acid and di- and poly-basic acids such as succinic, glutaric, adipic, sebacic or tricarballylic acid.  A number of catalysts are specified, and the reaction may also be promoted by ultra-violet light with a photo-sensitizer, e.g. biacetyl, mercury, an alkyl iodide or acetone. Examples are given of the production of acids of high molecular weight from propionic, isobutyric, adipic and caprylic acids.  The alkali-metal and ammonium salts of the acids are useful as dispersing agents.  The alkaline-earth and heavy-metal salts of the acids may be used as components of corrosion-preventing compositions.  The acids may also be converted in known manner into amines, which may be used as starting materials for cationic surface-active agents. Specifications 471,590, 497,643, 578,584, 583,181, 584,795, [all in Group IV], 605,849 and 8070/40, as open to inspection under Sect. 91, are referred to.  The Specification as open to inspection under Sect. 91 refers to the treatment of palmitic acid and to the use of any mono-olefine, preferably one containing less than five carbon atoms. This subject-matter does not appear in the Specification as accepted.ALSO:Carboxylic acids containing a long chain of -CH2- groups are obtained by the action of ethylene on carboxylic acids which are free from olefinic or acetylenic unsaturation and have at least one a -hydrogen atom, the reaction being effected at a raised temperature and pressure in the presence of a catalyst capable of converting ethylene under these conditions into a solid polymer.  The effect of the reaction is to convert an acid RCOOH into an acid R(CH2)n COOH, where n may be 6-50 or more.  Specified acids which may be treated are acetic, propionic, butyric, valeric and homologous acids, e.g. octanoic, decanoic, lauric or myristic acid, isobutyric acid, butane-2-carboxylic acid, pentane-3-carboxylic acid and di- and poly-basic acids such as succinic, glutaric, adipic, sebacic or tricarballylic acid.  Specified catalysts are organic peroxy compounds such as benzoyl peroxide, acetyl peroxide, propionyl, butyryl, lauroyl and acetylbenzoyl peroxides, dimethyl, diethyl and dipropionyl peroxides, and benzaldehyde peroxides; hydrazine compounds such as hydrazine sulphate or hydrochloride, dibenzoyl-hydrazine, and semi-carbazide hydrochloride; perhalo compounds such as hexachlorethane and octachlorpropane; per-salts such as alkali-metal and ammonium persulphates, perborates and percarbonates; organometallic compounds such as tetraethyl lead; oxygen in low concentration, e.g. 2-10 parts per million, and compounds containing active halogen, such as sodium N-chloro-p-toluene sulphonamide, calcium hypochlorite, N-chloroamides, N - chloroalkenesulphonamides, N-chlorourea, and potassium chlorate with manganese dioxide.  The reaction may also be promoted by ultra-violet light with a photosensitizer, e.g. biacetyl, mercury, an alkyl iodide or acetone.  The reaction may be effected at 50-400 DEG  C. and 100-2000 atm. pressure in the presence or absence of a diluent, such as tert.-butyl methyl ether, methyl pivalate, benzene or chlorobenzene.  Examples are given of the production of acids of high molecular weight from propionic, isobutyric, adipic and caprylic acids.  The acids and their salts are useful as compounding ingredients and milling aids in the processing of natural or synthetic rubber, and as anti-tack agents in the calendering of plastics.  The alkali-metal and ammonium salts of the acids are useful also as dispersing and wetting agents, e.g. in textile dyeing and finishing processes or for wetting sulphur; solutions or dispersions of these salts in dry-cleaning fluids, such as naphtha and polychloro compounds, may be used as dry-cleaning agents.  The alkaline-earth and heavy-metal salts of the acids may be incorporated with waxes or greases or used as components of corrosion-preventing, water-proofing or water-repellent compositions.  The acids may also be esterified with short-chain alcohols, to yield products useful as plasticisers and lubricants, or with long-chain alcohols or glycol to yield products useful as waxes or additions to waxes. The N-hydroxy methylamides of the acids, or the reaction products of these amides with salts of tertiary amines, are useful as water-repellents.  The acids may also be converted in known manner into chlorides, anhydrides, alcohols, sulphates, mercaptans, nitriles and amines. The chlorides and anhydrides may be used as water-repellent finishes for paper and textiles, the alcohols may be used as wax components or as starting materials for sulphate detergents, the mercaptans may be used as modifiers for synthetic rubber preparation and other vinyl polymerizations, and the amines may be used as starting materials for cationic surface-active agents.  Specifications 471,590, 497,643, 578,584, 583,181, 584,795, 605,849, [Group IV (b)], and 8070/40 (as open to inspection under Sect. 91) are referred to.  The Specification as open to inspection under Sect. 91 refers to treatment of palmitic acid and to the use of any mono-olefine, preferably one containing less than five carbon atoms.  This subject-matter does not appear in the Specification as accepted.ALSO:Carboxylic acids containing a long chain of -CH2- groups are obtained by the action of ethylene on carboxylic acids which are free from olefinic or acetylenic unsaturation and have at least one a -hydrogen atom, the reaction being effected at a raised temperature and pressure in the presence of a catalyst capable of converting ethylene under these conditions into a solid polymer.  The effect of the reaction is to convert an acid RCOOH into an acid R(CH2)nCOOH, where n may be 6-50 or more.  Specified acids which may be treated are acetic, propionic, butyric, valeric and homologous acids, e.g. octanoic, decanoic, lauric or myristic acid, isobutyric acid, butane - 2 - carboxylic acid, pentane-3-carboxylic acid and di-and poly-basic acids such as succinic, glutaric, adipic, sebacic or tricarballylic acid.  Specified catalysts are organic peroxy compounds such as benzoyl peroxide, acetyl peroxide, propionyl, butyryl, lauroyl and acetylbenzoyl peroxides, dimethyl, diethyl and dipropionyl peroxides, and benzaldehyde, peroxides; hydrazine compounds such as hydrazine sulphate or hydrochloride, dibenzoylhydrazine and semicarbazide hydrochloride; perhalo compounds such as hexachlorethane and octachlorpropane; per-salts such as alkali-metal and ammonium per-sulphates, perborates and percarbonates; organo-metallic compounds such as tetraethyl lead; oxygen in low concentration, e.g. 2-10 parts per million, and compounds containing active halogen, such as sodium N-chloro-p-toluenesulphonamide, calcium hypochlorite, N-chloroamides, N-chloroalkanesulphonamides, N-chlorourea and potassium chlorate with manganese dioxide.  The reaction may also be promoted by ultra-violet light with a photosensitizer, e.g. biacetyl, mercury, an alkyl iodide or acetone.  The reaction may be effected at 50-400 DEG  C. and 100-2000 atm. pressure in the presence of absence of a diluent, such as tert.-butyl methyl ether, methyl pivalate, benzene or chlorobenzene.  Examples are given of the production of acids of high molecular weight from propionic, isobutyric, adipic and caprylic acids.  The acids and their salts are useful as compounding ingredients and milling aids in the processing of natural or synthetic rubber, and as anti-tack agents in the calendering of plastics.  The alkali-metal and ammonium salts of the acids are useful also as dispersing and wetting agents, e.g. in textile dyeing and finishing processes or for wetting sulphur; solutions or dispersions of these salts in dry-cleaning fluids, such as naphtha and polychloro compounds, may be used as drycleaning agents.  The alkaline-earth and heavy-metal salts of the acids may be incorporated with waxes or greases or used as components of corrosion-preventing, water-proofing or water-repellent compositions.  The acids may also be esterified with short-chain alcohols, to yield products useful as plasticisers and lubricants, or with long-chain alcohols or glycol to yield products useful as waxes or additions to waxes. The N-hydroxymethylamides of the acids, or the reaction products of these amides with salts of tertiary amines, are useful as water-repellents. The acids may also be converted in known manner into chlorides, anhydrides, alcohols, sulphates, mercaptans, nitriles and amines. The chlorides and anhydrides may be used as water-repellent finishes for paper and textiles, the alcohols may be used as wax components or as starting materials for sulphate detergents, the mercaptans may be used as modifiers for synthetic rubber preparation and other vinyl polymerizations, and the amines may be used as starting materials for cationic surface-active agents.  Specifications 471,590, 497,643, 578,584, 583,181, 584,795, 605,849 and 8070/40 (as open to inspection under Sect. 91) are referred to.  The Specification as open to inspection under Sect. 91 refers to treatment of palmitic acid and to the use of any mono-olefine, preferably one containing less than five carbon atoms.  This subject-matter does not appear