Patent GB-845286-A (GB)
Title: New polyglycol ether derivatives and process for their manufacture
IPC: D06P1/607
Filed: 1956-10-18
Abstract: The invention comprises polyethyleneglycol-amines of the formula R-NAB, where R is an unbranched aliphatic hydrocarbon radical of at least 20 carbon atoms, A is -(CH2CH2O)xH, and B is H or -(CH2CH2O)yH, the sum of x and y being at least 10 and preferably 20 or more, e.g. 50-100.  These are made by reacting ethylene oxide or a polyethyleneglycol halide with RNH2 which may be present (to the extent of 10% or more) in a mixture containing primary amines of lower chain length, preferably at least 16 carbon atoms.  The reaction with ethylene oxide is carried out in the presence of a catalyst such as an alkali metal or its hydroxide, carbonate or acetate.  The products can be converted into salts, e.g. acetates or quaternary salts. In examples, (1) and (3) ethylene oxide is reacted with a mixture of stearylamine, arachidylamine and behenylamine, with or without palmitylamine; (11) a similar mixture is reacted with a polyethyleneglycol chloride of mol. wt. 610; (12) arachidylamine is reacted with a polyethyleneglycol chloride of mol. wt. 1250; and (6) arachidylamine or behenylamine is reacted with ethylene oxide.  Other suitable starting materials are lignocerylamine montanylamine, brassidylamine, erucylamine and the mixture of amines obtained by hydrolyzing, ammonating and hydrogenating natural fat or oils which contain appropriate carbon chains, e.g. rape seed, whale, cod-liver, merhaden and sardine oils.  Uses.  As levelling or stripping agents for wool dyestuffs.ALSO:The invention comprises amines of the formula R-NAB, where R is an unbranched aliphatic hydrocarbon radical of at least 20 carbon atoms, A is -(CH2CH2O)xH, and B is H or -(CH2 CH2O)H, the sum of x and y being at least 10, and their preparation by reacting RNH2 with ethylene oxide or a polyglycol halide.  The starting material can be a mixture containing primary amines of lower chain length (preferably at least 16 carbon atoms) provided at least 10% have 20 or more carbon atoms.  Such mixtures are obtained by hydrogenating (e.g. with a cobalt catalyst) the nitriles of fatty acids derived from natural oils and fats such as rape-seed oil, whale oil, cod-liver oil, menhaden oil and sardine oil.  The reaction with ethylene oxide is carried out in the presence of a catalyst such as an alkali metal or its hydroxide, carbonate or acetate, preferably to introduce 20 or more, e.g. 50-100 ethylene oxide residues.  The products can be converted into salts, e.g. acetates or quaternary salts.  In Examples (1) ethylene oxide is reacted with a mixture of stearylamine, arachidylamine and behenylamine, with or without palmitylamine, (2) a similar mixture is reacted with a polyglycol chloride, (3) arachidylamine is reacted with a polyglycol chloride and (4) arachidylamine or behenylamine is reacted with ethylene oxide.  Other suitable starting materials are lignocerylamine, montanylamine, brassidylamine and erucylamine.  The last named can be obtained (mixed with higher saturated amines) by reesterifying rape-seed oil with methanolic hydrochloric acid, separating off the methyl ester, catalytically reacting it with ammonia to give erucic nitrile and reducing the latter with sodium and butanol.ALSO:The equilibrium of the distribution of a dyestuff between an aqueous liquor and a basic nitrogenous fibre is shifted by incorporating in the liquor a compound of the formula R-NAB, where R is an unbranched aliphatic hydrocarbon radical of at least 20 carbon atoms, A is -(CH2CH2O)x H, and B is H or- (CH2CH2O)y H, the sum of x and y being at least 10 and preferably 20 or more, e.g. 50-100.  There may also be present amines of the above formula where R has less than 20 carbon atoms (preferably 16 or more) as long as there are at least 10% of the C20 upwards amines.  Dyestuffs that are rapidly absorbed by the fibre can be induced to give level dyeings by adding one of the present products to the dyebath or by pretreating the fibre therewith This process is particularly suitable when dyeing wool with complex chromium or cobalt compounds containing 1 atom of metal to 2 molecules of dyestuff, in which there is 0 or 1 carboxylic or sulphonic acid group, using a weakly acid bath.  The products can also be used for stripping or lightening dyeings, if desired in combination with other agents such as sodium hydrosulphite.  In examples, (1) wool is dyed in an acetic acid bath containing the chromium derivative of the dyestuff 2-aminophenol -5-sulphonamide --> 5 : 8-dichloro -1- naphthol and the polyglycol derivatives of a mixture of palmitylamine, stearylamine, arachidylamine and behenylamine; chlorinated and unchlorinated wool can thus be dyed simultaneously to the same blue shade; (2) wool is dyed in an ammonium sulphate bath with the cobalt derivative of the dyestuff 2-aminophenol -4- sulphonamide --> 5 : 8-dichloro -1- naphthol; during the dyeing there are added the polyglycol mixture as in (1) and acetic acid; (3) wool is dyed in a sulphuric acid bath containing the dyestuffs 1-naphthylamine --> 1-naphthol-3 : 6-disulphonic acid, aniline --> 1-(p-sulphophenyl) -3- methyl -5- pyrazolone, Methyl Violet and 4 : 41 -bis -(ethylbenzylamino) -311 -hydroxy -triphenylmethane -411 , 611 -disulphonic acid (mixed calcium carbinol salt), and also the polyglycol derivatives of a mixture of stearylamine, arachidylamine and behenylamine; (4) wool dyed with the dyestuff of (1) is stripped by using the polyglycol derivatives as in (1).  Other suitable dyestuffs and polyglycol-amines are mentioned.