Patent GB-753193-A (GB)
Title: Improvements in or relating to the production of glycidyl ethers of polyhydric phenols
IPC: C08G59/06
Filed: 1954-10-18
Abstract: A glycidyl ether of a polyhydric phenol is prepared by adding an aqueous solution of alkali metal hydroxide containing at least 15 per cent by weight of the hydroxide to a solution of a polyhydric phenol in at least 3 mols. of epichlorhydrin per phenolic hydroxyl equivalent of the phenol, the total amount of alkali metal hydroxide being about one mol. per phenolic hydroxyl equivalent of the phenol, continuously distilling water and epichlorhydrin from the reaction mixture, separating the distilled products from each other and returning only the epichlorhydrin to the reaction mixture, the rate of addition of the hydroxide solution and the distillation rate being regulated so that the reaction mixture contains from about 0.3 to 2.0 per cent by weight of water.  The phenelic hydroxyl equivalent is the molecular weight of the phenol in any given units divided by the number of phenolic hydroxyl groups in the molecule.  The temperature of the reaction mixture is maintained at about 105-115 DEG  C. at atmospheric pressure but sub- or super-atmospheric pressures may be used.  The vapours may be separated by condensation into layers or by solvent extraction of the condensate.  Polyhydric phenols specified are resorcinol, hydroquinone, methyl resorcinols, phloroglucinol, 1:5 - dihydroxynaphthalene, 4:41 - dihydroxydiphenyl, bis - (4 - hydroxyphenyl-methane, 1:1 - bis - (4 - hydroxyphenyl) ethane, 1:1 - bis - (4 - hydroxyphenyl) isobutane, 2:2 - bis - (2- or 4 - hydroxyphenyl) propane, 2:2-bis - (4 - hydroxyphenyl) butane, 2:2 - bis - (4 - hydroxy - 2 - methylphenyl) propane, 2:2 - bis(2 - hydroxy - 4 - tert.-butylphenyl) propane, 2:41 - dihydroxy - diphenyldimethylmethane, 2:2 - bis - (2 - chloro - 4 - hydroxyphenyl) propane, 2:2 - bis - (2 - hydroxynaphthyl) pentane, 2:2 - bis - (2:5 - dibromo - 4 - hydroxyphenyl) butane, 4:41-dihydroxybenzophenone, 1:3 - bis - (4 - hydroxyphenyloxy) - 2 - hydroxypropane, 3 - hydroxyphenyl salicylate, 4-salicoylamino-phenol, complex polyhydric phenols obtainable by acid catalysed condensation of phenol, p-cresol or other substituted phenols with formaldehyde, acetaldehyde or crotonaldehyde, and condensates of phenols with cardanol, aliphatic diols or unsaturated fatty oils.  The reaction mixture may also contain inert solvents such as toluene or xylene.  The excess of epichlorhydrin, 5-12 mols. per phenolic hydroxyl equivalent may be used, suppresses the formation of condensed or cross-linked products. When all the hydroxide solution has been added distillation is continued until the mixture is substantially anhydrous.  The unreacted epichlorhydrin is then removed by distillation, and the residue treated with a solvent, e.g. toluene, filtered to remove alkali metal chloride and distilled, or the anhydrous reaction mixture is filtered and the epichlorhydrin is distilled.  In examples: (1) 2:2-bis-(4-hydroxyphenol) propane (1.5 mols.) and epichlorhydrin (15 mols.) were heated with addition of sodium hydroxide solution (3.0 mols.) during 3 1/2 hours, excess epichlorhydrin was then removed and the residue treated with toluene and distilled as described above; (2) as in (1) but 2 per cent excess of sodium hydroxide used; (3) as in (2) but the anhydrous mixture was filtered and epichlorhydrin distilled; (4) a glycidyl ether of a polyhydric phenol (obtained by condensing phenol with cardanol) was prepared.