Patent GB-605849-A (GB)
Title: Improvements in or relating to the manufacture of long chain carboxylic acids
IPC: C11C1/00
Filed: 1946-03-18
Abstract: Carboxylic acids containing a long chain of -CH2- groups obtained by reacting ethylene and an organic carboxylic acid free from olefinic and acetylenic unsaturation and having at least one alpha hydrogen atom at a temperature of 50-400 DEG  C. and under superatmospheric pressure in the presence of a catalyst having the >C=N- group and which is derived from an aldehyde or a ketone (see Group IV (b)) may be converted to their sodium, other alkali metal, ammonium or substituted ammonium salts which show detergent and emulsifying properties.  Specified carboxylic acids for the reaction are acetic, propionic, butyric, isobutyric, valeric, octanoic, decanoic, lauric and myristic acids, butane-2-carboxylic acid, pentane-3-carboxylic acid and succinic, glutaric, adipic, sebacic and tricarballylic acids. Specification 471,590, 497,643, 578,584, 583,181, 584,795, [all in Group IV], 605,848 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 subjecting ethylene and an organic carboxylic acid free from olefinic and acetylenic unsaturation and having at least one alpha hydrogen atom to a temperature between 50 DEG  and 400 DEG  C. and superatmospheric pressure preferably between 100 and 2000 atmospheres in the presence of a catalyst having the >C=N- group and which is derived from an aldehyde or a ketone.  An acid H.R1.R2.C.COOH is thus converted to an acid H(C2H4)nR1.R2.C.COOH, where R1 and R2 are hydrogen, monovalent hydrocarbon groups and carboxyl substituted monovalent hydrocarbon groups, and n may be 6-50 or more.  Specified acids which may be treated are acetic, propionic, butyric, isobutyric, valeric and homologous acids, e.g. octanoic, decanoic, lauric and myristic acids, butane-2-carboxylic acid and pentane-3-carboxylic acid, also di- and poly-basic acids such as succinic, glutaric, adipic, sebacic and tricarballylic acids.  Specified catalysts include azines such as benzalazine, heptaldazine and diphenylketazine, oximes such as d-camphor oxime, acetone oxime, alpha benzil dioxime, butyraldehyde oxime, alpha-benzoin oxime, dimethylglyoxime; hydrazones such as benzaldehyde phenyl hydrazone, phenyl hydrazones of cyclohexanone, cyclopentanone, acetophenone, menthone, camphor and benzophenone; semicarbazones such as those of acetone, methyl ethyl ketone, diethyl ketone, diacetyl, cyclopentanone, cyclohexanone, acetophenone, propiophenone, camphor and benzophenone; Schiff's bases such as benzalaniline, benzal-p-toluidine, benzal-o-toluidine, benzaldehyde derivatives of methylamine, ethylamine and heptylamine, acetaldehyde anil, acetone anil, isobutyraldehyde anil and heptaldehyde anil.  The ethylene used may contain small quantities of ethane, propane, nitrogen, hydrogen, carbon dioxide or oxygen.  The oxygen may function as a catalyst and is employed preferably in less than 10 parts per million by volume.  A diluent or solvent may be used, such as tert.-butyl methyl ether, methyl pivalate, benzene, chlorobenzene, isooctane and pentamethylethane.  Examples are given for the production of high molecular weight acids from isobutyric acid and ethylene in the presence of benzalazine, diphenyl ketazine, d-camphor oxime, acetone semicarbazone, benzaldehyde phenyl hydrazone and benzalaniline respectively as catalyst, also from propionic acid and ethylene using benzalazine as catalyst.  The process may be carried out continuously.  The acids may be esterified with short-chain or long-chain alcohols or glycol or may be converted via the amide to N-hydroxymethyl amides which may be reacted with a tertiary amine salt to give water-repellents.  The acids may also be converted in known manner into the acid chlorides, anhydrides, alcohols, sulphates, chlorides, mercaptans, nitriles and amines.  Reference is also made to the sodium, other alkali metal, ammonium or substituted ammonium salts which have detergent, emulsifying and wetting properties and the acids themselves, their calcium and other alkaline earth salts, aluminium and zinc salts, heavy metal salts, acid chlorides, anhydrides, alcohols, mercaptans and amines have the same applications as the corresponding compounds in Specification 605,848. Specifications 471,590, 497,643, 578,584, 583,181, 584,795 and 8070/40 (as open to inspection under Sect. 91) also 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 subjecting ethylene and an organic carboxylic acid free from olefinic and acetylenic unsaturation and having at least one alpha hydrogen atom to a temperature between 50 DEG  and 400 DEG  C. and superatmospheric pressure preferably between 100 and 2000 atmospheres in the presence of a catalyst having the >C=N- group and which is derived from an aldehyde or a ketone (see Group IV (b)). An acid HR1R2C.COOH is thus converted to an acid H(C2H4)nR1R2C.COOH, where R1 and R2 are hydrogen, monovalent hydrocarbon groups and carboxyl substituted monovalent hydrocarbon groups, and n may be 6-50 or more.  The sodium, other alkali metal, ammonium or substituted ammonium salts have detergent, emulsifying and wetting properties and the acids themselves their calcium and other alkaline earth salts, aluminium and zinc salts, heavy metal salts, acid chlorides, anhydrides, alcohols, mercaptans and amines have the same applications as the corresponding compounds in Specification 605,848. Specifications 471,590, 497,643, 578,584, 583,181, 584,795 and 8070/40, as open to inspection under Sect. 91, also 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.