Patent GB-762122-A (GB)
Title: A process for the manufacture of condensation products of unsaturated fatty acids or esters of the same
IPC: C11C3/00
Filed: 1954-02-19
Abstract: Condensation products, suitable for use in the lacquer industry, are produced by heating unsaturated non-conjugated fatty acids or esters thereof, either or not in admixture with saturated fatty acids and/or a minor proportion of unsaturated conjugated fatty acids or esters, with dienophylic compounds in the presence of iodine or a compound capable of generating iodine, such as hydriodic acid or its salts with organic bases, iodine chloride, bromides or fluorides, iodoform, or zinc iodide, preferably in a proportion of 0.1 to 2 per cent based on the fatty acids.  The reaction temperature may range from 120 DEG to 300 DEG  C., preferably from 175 DEG  to 250 DEG  C.  The term "fatty acid" means fatty acids having 6 to 24 carbon atoms.  The starting material may comprise fatty acids having one or more double bonds, e.g. oleic, linoleic or linolenic acids.  The said mixtures of fatty acids may also contain unsaturated hydroxy fatty acids and dimers or polymers of unsaturated fatty acids.  Suitable esters are triglycerides such as animal or vegetable fats and oils.  Said oils may be partly hydrogenated, oxidized and/or polymerized.  The fatty acid mixtures may be subjected to such preliminary treatments as pressing, crystallization or distillation. Suitable dienophylic compounds are maleic anhydride, maleic acid and esters such as diethyl maleinate, itaconic acid, mesaconic acid, citraconic acid, acrylic acid, methacrylic acid, methylmethacrylate, furfural, allyl chloride, mesityl oxide and styrene.  Mixtures of different dienophylic compounds may be used simultaneously or successively.  It is advantageous to add the catalyst at a temperature at which the mixture of fatty acids or their esters and the dienophylic compound has become homogeneous, preferably at reaction temperature.  The condensation may be effected in the presence of a high-boiling inert solvent such as "Tetralin," "Decalin," (Registered Trade Marks) or other hydrocarbons, or ketones.  When the reaction is finished, iodine may be removed by distillation or by treatment with activated zinc and water or with a solution of sulphate or thiosulphate and maleic anhydride may be removed by distillation or washing with hot water.  The products may be used as such or the unreacted fatty acids or esters may be separated from the condensation products by distillation and/or treatment with solvents such as aliphatic or cycloaliphatic hydrocarbons, e.g. petroleum ether. The condensation products may be mono-, di- or tri-adducts depending on the number of double bonds in the starting material. By condensing a mixture of fatty acids with not more than 200 mol. per cent, preferably not more than 150 mol. per cent, of dienophylic compound, calculated on the unsaturated fatty acids, the reaction may be interrupted when only the mono-adducts have been formed.  The condensation products may be esterified with glycols or diamines.  Detailed examples are given in which maleic anhydride is condensed with fatty acids from sunflower seed oil, cotton seed oil, soya bean oil or linseed oil, with olein, or with a mixture of oleic acid and saturated acids, in the presence of iodine, hydriodic acid, the hydriodic acid salt of pyridine, or zinc iodide.  Specifications 500,348, 647,352, 762,123 and 762,124, [both in Group IV (b)], are referred to.ALSO:Condensation products, suitable for use in the lacquer industry, are produced by heating unsaturated non-conjugated fatty acids or esters thereof, either or not in admixture with saturated fatty acids and/or a minor proportion of unsaturated conjugated fatty acids or esters, with dienophylic compounds in the presence of iodine or a compound capable of generating iodine, such as hydriodic acid or its salts with organic bases, iodine chlorides, bromides or fluorides, iodoform or zinc iodide, preferably in a proportion of 0.1 to 2 per cent based on the fatty acids.  The reaction temperature may range from 120 DEG  to 300 DEG  C., preferably from 175 DEG  to 250 DEG  C.  The term " fatty acid " means fatty acids having 6 to 24 carbon atoms.  The starting material may comprise fatty acids having one or more double bonds, e.g. oleic, linoleic or linolenic acids.  The said mixtures of fatty acids may also contain unsaturated hydroxy fatty acids and dimers or polymers of unsaturated fatty acids.  Suitable esters are triglycerides such as animal or vegetable fats and oils.  Said oils may be partly hydrogenated, oxidized and/or polymerized.  The fatty acid mixtures may be subjected to such preliminary treatments as pressing, crystallization or distillation.  Suitable dienophylic compounds are maleic anhydride, maleic acid and esters, such as diethyl maleinate, itaconic acid, mesaconic acid, citraconic acid, acrylic acid, methacrylic acid, methylmethacrylate, furfural, allyl chloride, mesityl oxide and styrene.  Mixtures of different dienophylic compounds may be used simultaneously or successively. It is advantageous to add the catalyst at a temperature at which the mixture of fatty acids or their esters and the dienophylic compound has become homogeneous, preferably at reaction temperature.  The condensation may be effected in the presence of a high-boiling inert solvent such as " Tetralin ", " Decalin " (Registered Trade Marks) or other hydrocarbons, or ketones.  When the reaction is finished, iodine may be removed by distillation or by treatment with activated zinc and water or with a solution of sulphite or thiosulphate, and maleic anhydride may be removed by distillation or washing with hot water.  The products may be used as such or the unreacted fatty acids or esters may be separated from the condensation products by distillation and/or treatment with solvents such as aliphatic or cycloaliphatic hydrocarbons, e.g. petroleum ether.  The condensation products may be mono-, di- or tri-adducts depending on the number of double bonds in the starting material.  By condensing a mixture of fatty acids with not more than 200 mol. per cent, preferably not more than 150 mol. per cent, of dienophylic compound, calculated on the unsaturated fatty acids, the reaction may be interrupted when only the mono-adducts have been formed.  The condensation products may be esterified with glycols or diamines.  Detailed examples are given in which maleic anhydride is condensed with fatty acids from sunflower seed oil, cotton seed oil, soya bean oil or linseed oil, with olein, or with a mixture of oleic acid and saturated acids, in the presence of iodine, hydriodic acid, the hydriodic acid salt of pyridine, or zinc iodide.  Specifications 500,348, [Group IV], 647,352, [Group IV (a)], 762,123 and 762,124 are referred to.