Patent GB-740840-A (GB)
Title: Improvements in or relating to anion exchange resins
IPC: B01J41/04
Filed: 1953-06-04
Abstract: An anion-exchange resin containing basic nitrogen atoms and etherified aromatic hydroxyl groups but no free aromatic hydroxyl groups is made by reacting in an acid aqueous medium 1 mol. of an etherified aromatic hydroxyl compound which contains a basic nitrogen-containing group and/or an active halogen atom containing group and which is free from substituents in at least two of the positions ortho and para to the etherified hydroxyl group, with at least 1 mol. of an aldehyde, continuing this reaction until a gel forms and heating the gel until a resin insoluble in dilute solutions of mineral acids is obtained, said resin being reacted with a basic nitrogen-containing compound when the etherified aromatic hydroxyl compound used for the production of the resin contains an active halogen-containing group.  Specified aromatic ethers are alkyl aryl ethers containing a reactive halogen atom attached to the aliphatic group, e.g. phenoxyethyl bromide; the reaction products of epichlorhydrin and mono- or di-hydroxy benzenes; alkaryl, diaryl and cyclic ethers containing a halogen methyl group on the aromatic nucleus; and aromatic and cyclic ethers containing aliphatic groups with activated halogen atoms, suitable ethers being anisol, phenetol, diphenyl ether, diphenylene dioxide and diphenylene oxide.  Basic groups may be introduced into these ethers by primary, secondary or tertiary amines (many specified), or by ammonia.  When condensing with formaldehyde an additional resin-forming component may be included, e.g. phenyl methyl ether, naphthyl methyl ether, pyrocatechol diethyl ether, diphenyl oxide, diphenylene dioxide, xylene, naphthalene or anthracene oil or the chloromethyl derivatives of these compounds.  In the latter case, the reactive halogen in the resin may be reacted with organic bases to introduce further anion-exchange groups.  In examples: (1) the quaternary base obtained by reacting phenol, trimethylamine and epichlorhydrin is condensed with paraformaldehyde in presence of sulphuric acid.  Instead of phenol, resorcinol or catechol may be used.; (2) the reaction product of phenol, trimethylamine and epichlorhydrin is condensed with diphenyl ether and paraformaldehyde in presence of sulphuric acid; (3) the quaternary ammonium salt obtained by reacting phenoxy ethyl bromide with trimethylamine is condensed with diphenyl ether and paraformaldehyde in presence of sulphuric acid.  Instead of phenoxy ethyl bromide there may be used phenoxy propyl bromide, phenoxy butyl bromide or phenoxy isobutyl bromide; (4) hydrogen chloride is introduced into an emulsion of diphenyl ether and paraformaldehyde in sulphuric acid to produce a chloromethylation product which is condensed with paraformaldehyde and the quaternary salt obtained by reacting trimethylamine with chloromethyl diphenyl ether.  The resultant resin may be after treated with trimethylamine; (5) hydrogen chloride is introduced into an emulsion containing diphenyl ether, paraformaldehyde and sulphuric acid and the reaction product condensed with paraformaldehyde.  The resultant resin is reacted with trimethylamine; (6) hydrogen chloride is passed into a mixture of naphthalene, paraformaldehyde and sulphuric acid.  Then (trimethyl)-3-phenoxy-2-hydroxypropyl ammonium chloride is added, the mixture condensed with paraformaldehyde and the resulting resin heated with trimethylamine; (7) phenoxyethyl-trimethyl-ammonium chloride (obtained from phenoxyethyl chloride and trimethylamine) is condensed with diphenyl ether and paraformaldehyde.  The resulting resin is reacted with trimethylamine; (8) phenoxyethyl chloride and polyethylene polyamine bases are reacted and ethylene chloride introduced to induce the formation of ethylene bridges between nitrogen atoms.  The product is then condensed with formalin, paraformaldehyde and diphenyl ether in presence of sulphuric acid; (9) the condensation product of phenoxyethyl chloride and hexamethylene diamine is neutralized with caustic soda, converted into the sulphate with sulphuric acid and condensed with paraformaldehyde in presence of sulphuric acid; (10) phenoxyethyl piperidine (obtained from phenoxyethyl chloride and piperidine) is condensed with paraformaldehyde and anisol in presence of sulphuric acid; (12) mono- and/or di - phenoxyethyldimethylethylenediamine (obtained from phenoxyethyl chloride and dimethyl-ethylene diamine) are condensed with paraformaldehyde in presence of sulphuric acid. When using the mono-amine, naphthalene or an aromatic ether may be included as an additional reactant.