Patent GB-813495-A (GB)
Title: Ethers of polyoxyalkylene glycols
Inventor: HEFNER ROBERT EUGENE
IPC: C07C41/03
Filed: 1956-12-17
Abstract: Sodium and potassium salts of monoethers of polyoxyalkylene glycols are prepared by adding at least one of the 1 : 2-epoxides of ethylene, propylene, or butylene to a well agitated solution of the sodium or potassium salt of a monohydric phenol or aliphatic alcohol having from 1 to 20 carbon atoms in a relatively inert diluent, the reaction being carried out in substantially moisture-free conditions at 60 DEG  to 200 DEG  C. until at least 5 mols. of the 1 : 2-epoxy compound have been added for each mol. of the sodium or potassium salt.  The monohydroxy compounds may bear alkoxy substituents, and may be a primary, secondary or tertiary alkanol, alkoxy alkanol, phenol, alkoxy phenol or alkyl phenol. The sodium or potassium salt may be prepared in the same reaction vessel prior to the reaction with the epoxy compound by treating the hydroxy compound with at least 0.8 mols. of sodium or potassium under moisture free conditions in the presence of an inert diluent at a temperature between - 10 DEG and 150 DEG  C.  The diluent may be diisopropyl ether, dioxane, n-hexane, cyclohexane, benzene or toluene.  The reaction may be carried out at slightly elevated pressure, e.g. up to 10 atmospheres. The product may be neutralized, e.g. with anhydrous or aqueous hydrogen chloride, to give the mono-ether of the polyoxyalkylene glycol which may be worked up by extraction and distillation or the product may be treated with an alkyl halide such as methyl chloride, preferably at 60 DEG  to 160 DEG  C. to give a di-ether of the polyoxyalkylene glycol.  In the examples sodium is reacted with the monohydroxy compound in a steel vessel in the presence of toluene at about 120 DEG  C. and 3-4 atmos. pressure, the hydrogen evolved is vented off, and the epoxide is added at about 140 DEG  C. and 3-7 atmos. pressure until the desired chain length is obtained.  When a diether is desired the salt of the monoether is heated with sodium until no more hydrogen is evolved and then treated with an excess of gaseous methyl chloride at 100 DEG  to 110 DEG  C. and 4-7 atmos. The examples describe the preparation of (3) polyoxypropylene glycol n-butyl methyl ether; (7) polyoxypropylene glycol phenyl methyl ether; (8) polyoxybutylene glycol sec.-butyl methyl ether and (1), (2), (4), (5), (6), (9) polyoxypropylene glycol sec.-butyl methyl ether where (1), (2) various ratios of epoxide to sec.-butanol are used, (4), (5) a comparison is given with ethers not prepared in accordance with the invention, and (6) various diluents are used. Some physical properties of these polymeric diethers are given.ALSO:Sodium and potassium salts of monoethers of polyoxyalkylene glycols are prepared by reacting at least one of the 1 : 2 epoxides of ethylene, propylene or butylene with the sodium or potassium salt of a monohydric phenol or aliphatic alcohol having from 1 to 20 carbon atoms and containing only carbon, hydrogen and oxygen in the molecule with no other functional group other than the one hydroxy group, the reaction being carried out in substantially moisture-free conditions in the temperature range of 60 DEG  to 200 DEG  C. by adding the 1 : 2 epoxy compound to a well-agitated solution of the sodium or potassium salt of the monohydroxy compound in a diluent which is relatively inert both to the sodium or potassium and the 1 : 2 epoxy compound, until at least 5 mols. of the 1 : 2 epoxy compound have been added for each mol. of the sodium or potassium salt of the monohydroxy compound. The monohydroxy compounds used may bear alkoxy substituents and compounds such as primary, secondary and tertiary alkanols and alkoxy alkanols and phenol, alkoxy phenols and alkyl phenols may be used.  The sodium or potassium salt may be prepared in the same reaction vessel prior to the reaction with the epoxy compound by treating the hydroxy compound with at least 0.8 mol., preferably about 1 mol., of sodium or potassium under moisture-free conditions in the presence of an inert diluent at a temperature between - 10 DEG  and 150 DEG  C.  The diluent may be a compound such as di-isopropyl ether, dioxane, n-hexane, cyclohexane, benzene or toluene.  The 1 : 2 epoxy compound is added to a solution of the salt of the monohydroxy compound which is preferably heated to a temperature between 110 DEG  and 140 DEG C. until at least 5 mols. of epoxide have been added.  The reaction may be carried out at slightly elevated pressure, e.g. up to 10 atmospheres, to contain the reactants.  The reaction product, which contains the salt of the polyoxyalkylene glycol mono-ether may be neutralized, e.g. with anhydrous or aqueous hydrogen chloride, to give the mono-ether of the polyoxyalkylene glycol which may be worked up by extraction and distillation or the reaction product may be treated with an alkyl halide such as methyl chloride, preferably at a temperature between 60 DEG  and 160 DEG  C. to give a di-ether of the polyoxyalkylene glycol.  In the examples sodium is reacted with the monohydroxy compound in a steel vessel in the presence of toluene at about 120 DEG  C. and 3-4 atmos. pressure, the hydrogen evolved is vented off, and the epoxide is added at about 140 DEG  C. and 5-7 atmos. pressure until the desired chain length is obtained, when a diether product is desired the salt of the monoether is heated with sodium until no more hydrogen is evolved and then treated with an excess of gaseous methyl chloride at 100 DEG  to 110 DEG  C. and 4-7 atmos. until reaction is complete.  The examples describe the preparation of (3) polyoxypropylene glycol n-butyl methyl ether; (7) polyoxypropylene glycol phenyl methyl ether; (8) polyoxybutylene glycol sec.-butyl methyl ether and (1), (2), (4), (5), (6), (9), polyoxypropylene glycol sec.-butyl methyl ether where (1), (2) various ratios of epoxide to sec.-butanol are used, (4), (5) a comparison is given with ethers not prepared in accordance with the invention and (6) various diluents are used. Some physical properties of these polymeric diethers are given.