Patent GB-749112-A (GB)
Title: Manufacture of an etherification product of a polyglycidyl ether of a polyoxy compound with a higher monohydric alcohol
IPC: C07C41/03
Filed: 1952-12-19
Abstract: The invention comprises etherification products of polyglycidyl ethers of polyoxy compounds which contain at least 2 hydroxy groups and are free from other substituents capable of reacting with epoxide groups, with monohydric alcohols containing carbon chains of more than 10 carbon atoms.  They are made by reacting the alcohol with the ether advantageously at least one mol. of the former being used for a quantity of the latter corresponding to one epoxide gram equivalent. Polyoxy compounds mentioned are polyhydric aliphatic alcohols, e.g. glycol or glycerine, polyhydric, especially dihydric, phenols, e.g. resorcinol and particularly polyhydric polynuclear phenols, e.g. 4,41-dioxy-diphenyl-dimethyl methane.  The polyglycidyl ethers may be made by treating an aliphatic polyoxy compound with epichlorhydrin in the presence of sulphuric acid and treating the resulting polychlorhydrin ether with alkali or by treating an aromatic polyoxy compound with epichlorhydrin or dichlorhydrin preferably by reacting 1 mol. of 4,41-dioxy - diphenyl - dimethylmethane with at least 1-2 mols. of epichlorhydrin in the presence of aqueous alkali.  The products are mixtures consisting predominantly of polyglycidyl ethers with chains of different lengths carrying terminal epoxide groups and, if desired, intermediate hydroxyl groups.  Specified alcohols are undecyl, dodecyl, cetyl, octadecyl, myricyl, oleyl, linoleyl, linolenyl and abietinol and their glycol monoethers and glycerine diethers.  Alcohols made by the reduction of acids obtained by the oxidation of paraffin wax, alcohols obtained by the reduction of carbon monoxide and by the reduction, e.g. with sodium and alcohol, of triglyceride oils such as linseed, soya bean, dehydrogenated castor, poppy seed, hemp seed, cotton seed, coconut, cod liver, whale, menhaden, sperm and tall oil or tall oil esters may also be used.  The ethers used as starting material and the products are characterized by determining their content of epoxide and esterifiable groups and calculating their content of hydroxyl groups from these values.  The reaction with the alcohol may be effected at a low temperature in the presence of a catalyst such as boron trifluoride but is generally effected at high temperatures when the presence of a catalyst is preferred but is not essential.  Solvents, e.g. dioxane and inert gases, e.g. nitrogen, may be present. Sulphuric acid and sodium hydroxide are other catalysts mentioned. Reaction is generally continued until epoxide groups are no longer detected in the reaction mixture. The unreacted alcohols in the final products need not be removed. The products may be after treated with, e.g. phthalic or maleic anhydrides, abietic acid, linseed oil fatty acid, phenyl isocyanate, and condensation products containing methylol groups obtainable, e.g. from formaldehyde and phenol, urea or melamine and benzo-, aceto- or formo-guanamine, the methylol groups of the condensation product being at least partially etherified with an alcohol containing 1-4 C atoms per molecule.  If the reaction has been effected with unsaturated alcohols the final products may be polymerized before or after the after-treatments indicated above. The products and modified products may be used in lacquers, if desired, in admixture with alkyd resins, epoxide resins, styrenized oils and formaldehyde condensation products of phenol, urea or aminotriazines.  Examples are provided showing the use of certain of the above specified reactants in the preparation of the ethers and their after-treatments.  Anisole is an additional solvent used.  Specification 518,057 is referred to.ALSO:The invention comprises etherification products of polyglycidyl ethers of polyoxy compounds which contain at least 2 hydroxy groups and are free from other substituents capable of reacting with epoxide groups, with monohydric alcohols containing carbon chains of more than 10 carbon atoms.  They are made by reacting the alcohol with the ether advantageously at least one mol. of the former being used for a quantity of the latter corresponding to one epoxide gram equivalent. Polyoxy compounds mentioned are polyhydric aliphatic alcohols, e.g. glycol or glycerine, polyhydric, especially dihydric, phenols, e.g. resorcinol and particularly polyhydric polynuclear phenols, e.g. 4,41-dioxy-diphenyl-dimethyl methane.  The polyglycidyl ethers may be made by treating an aliphatic polyoxy compound with epichlorhydrin in the presence of sulphuric acid and treating the resulting polychlorhydrin ether with alkali or by treating an aromatic polyoxy compound with epichlorhydrin or dichlorhydrin preferably by reacting 1 mol. of 4,41-dioxy-diphenyl-dimethylmethane with at least 1.2 mols. of epichlorhydrin in the presence of aqueous alkali.  The products are mixtures consisting predominantly of polyglycidyl ethers with chains of different lengths carrying terminal epoxide groups and, if desired, intermediate hydroxyl groups.  Specified alcohols are undecyl, dodecyl, cetyl, octadecyl, myricyl, oleyl, linoleyl, linolenyl and abietinol and their glycol monoethers and glycerine diethers.  Alcohols made by the reduction of acids obtained by the oxidation of paraffin wax, alcohols obtained by the reduction of carbon monoxide and by the reduction, e.g. with sodium and alcohol, of triglyceride oils such as linseed, soya bean, dehydrogenated castor, poppy seed, hemp seed, cotton seed, coconut, cod liver, whale, menhaden, sperm and tall oil or tall oil esters may also be used.  The ethers used as starting material and the products are characterized by determining their content of epoxide and esterifiable groups and calculating their content of hydroxyl groups from these values.  The reaction with the alcohol may be effected at a low temperature in the presence of a catalyst such as boron trifluoride but is generally effected at high temperatures when the presence of a catalyst is preferred but is not essential.  Solvents, e.g. dioxane, and inert gases, e.g. nitrogen, may be present.  Sodium hydroxide and sulphuric acid are other catalysts mentioned.  Reaction is generally continued until epoxide groups are no longer detected in the reaction mixture.  The final products usually contain unreacted alcohols which need not be removed.  The products may be after-treated with e.g. phthalic or maleic anhydrides, abietic acid, linseed oil fatty acid, phenyl isocyanate, and condensation products containing methylol groups obtainable e.g. from formaldehyde and phenol, urea or melamine, benzo-, aceto- or formo-guanamine, the methylol groups of the condensation product being at least partially etherified with an alcohol containing 1-4 C atoms per molecule.  If the reaction has been effected with unsaturated alcohols the final products may be polymerized before or after the after-treatments indicated above.  The products may be used in lacquers.  Examples are provided showing the use of certain of the above specified components in the preparation of the ethers and their after-treatments.  Anisole is an additional solvent used.  Specification 518,057 is referred to.ALSO:Etherification products of polyglycidyl ethers of polyoxy compounds which contain at least 2 hydroxy groups and are free from other substituents capable of reacting with epoxide groups, with monohydric alcohols containing carbon chains of more than 10 carbon atoms and condensation products of these etherification products are used in lacquers.  Specified polyoxy compounds are glycol, glycerine, resorcinol and 4, 41-dioxy-diphenyl-dimethylmethane.  Specified alcohols are undecyl, dodecyl, cetyl, octadecyl, mericyl, oleyl, linoleyl, linolenyl and abietinol and their glycol monoethers and glycerine diethers.  Alcohols made by the reduction of acids obtained by the oxidation of paraffin wax, alcohols obtained by the reduction of carbon monoxide and by the reduction, e.g. with sodium and alcohol of triglyceride oil such as linseed, soya bean, dehydrogenated castor, poppy seed, hemp seed, cotton seed, coconut, cod liver, whale, menhaden, sperm and tall oil or tall oil esters may also be used.  After treatments may be effected with phthalic and maleic anhydrides, abietic acid, linseed oil fatty acid, phenyl isocyanate, and condensation products containing methylol groups obtainable, e.g. from formaldehyde and phenol, urea or melamine and benzo-, acetic- or formo-guanamine, the methylol groups of the condensation product being at least partially esterified with an alcocol containing 1-4 C. atoms per molecule.  If the reaction has been effected with unsaturated alcohols the final products may be polymerized before or after the above after treatments.  Details of the reaction and after treatments are given in Groups IV(a) and IV(b).  The etherification products and their condensation products may be used in lacquers admixed with substances such as alkyl and epoxide resins, styrenized oils and formaldehyde condensation products of phenol, urea or aminotriazines.  Etherification products derived from unsaturated alcohols from semi-drying oils yield with addition of driers such as a manganese, lead or cobalt drier, good oven-drying lacquers and those derived from highly unsaturated alcohols such as linseed oil fatty alcohol, have good oven-drying properties and good air-drying properties after the addition of a drier.  Examples illustrate the use of the products in lacquer compositions ingredients used other than those specified above being linseed, wood and stand oils, colophony, white spirit and toluene.