Patent GB-754679-A (GB)
Title: Improvements in or relating to polyoxyalkylated tert.-carbinamines
IPC: C11D1/44
Filed: 1954-07-07
Abstract: The invention comprises compounds of the formula <FORM:0754679/IV(a)/1> m being an integer from 3 to 100, n being 2 or 3 and R1, R2 and R3 being alkyl groups containing together 7 to 23 carbon atoms.  It also comprises a process for preparing polyoxyalkylated tert.-carbinamines by reacting a tert.-carbinamine of the formula <FORM:0754679/IV(a)/2> with an alkylene oxide of not more than 3 carbon atoms in the presence of a strong acid catalyst whereby an N-hydroxyalkyl-tert. carbinamine is formed and in the case of reacting tert.-octyl-and tert.-nonylamines some di-(hydroxyethyl)-tert.-alkylamine may also be formed, destroying the catalyst, removing any water from the amine and reacting it with an alkylene oxide of not more than 3 carbon atoms under the influence of a strong inorganic base as catalyst until 3 to 100 mols. of the alkylene oxide are taken up per mol. of amine.  Hydrohalic, sulphuric, arylsulphonic, alkanesulphonic, nitric, phosphoric and polyphosphoric acids and the hydrogen form of sulphonated cation-exchange resins are suitable catalysts.  Equivalent to the use of a hydrohalide is the reaction with ethylene chlorohydrin or bromohydrin which act as a source both of acid and ethylene oxide. When one (or, in some cases, two) molecules per molecule of amine have been reacted, the catalyst is destroyed by adding a base, salt and/or water are removed, 0.5 to 5 mol. per cent of the alkaline catalyst is added, and ethylene and/or propylene oxides are run in. Suitable catalysts are alkali metal hydroxides, alkali metals or alkali metal alcoholates.  Suitable carbinamines are 2 - amino - 2,4,4 - trimethylpentane, iso C8H17(C2H5)2C.NH2 and narrow mixtures of tert.-alkyl primary amines, e.g. C12H25NH2 to C15H31NH2 and C18H3NH2 to C27H49NH2.  In examples (1) technical tert. octadecylamine (with minor amounts of higher tertiary alkyl primary amines) is reacted in the presence of hydrochloric acid with ethylene oxide, and the N-hydroxyethyl-tert. octadecylamine obtained is reacted in the presence of potassium hydroxide with 10 mols. of ethylene oxide; (2) a mixture of tert.-carbinylamines from C18 to C24 is reacted as in (1) with a molecular proportion of ethylene oxide. Portions of the product are reacted with 5, 10, 20 and 50 mols., respectively, of ethylene oxide; (3) N-hydroxyethyl-tert.-carbinylamine (from the reaction of tertiary carbinylamines containing mainly a tert.-dodecyl group, with some higher groups up to tert.-pentadecyl) is reacted with 10 molecular proportions of ethylene oxide; (4) tert.-nonylamine (derived from a propylene trimer) is reacted in acid medium with ethylene oxide and and the recovered N-hydroxyethyl-tert.-nonylamine obtained is then reacted in alkaline medium with either 10 mols. of ethylene oxide or 20 mols. of a 50:50 mixture of ethylene and propylene oxides; similar products containing 4 to 50 ethylene oxide residues can be prepared; (5) tert.-octylamine is reacted under acid conditions with ethylene oxide to give N-mono- and di-(hydroxyethyl)-tert.-nonylamines which are separated and reacted 50 and about 45 molecular proportions of ethylene oxide. Alternatively, the mixed mono- and dihydroxy compounds can be reacted with ethylene oxide.  The products have surface-active properties.  They also have anti-corrosive properties, and, mixed with the initial carbinamines, inhibit the corrosive action of strong acids on metals.ALSO:The invention comprises compounds of the formula <FORM:0754679/IV(a)/1> m being an integer from 3 to 100, n being 2 or 3 and R1, R2 and R3 being alkyl groups containing together 7 to 23 carbon atoms.  It also comprises a process for preparing polyoxyalkylated tert.-carbinamines by reacting a tert.-carbinamine of the formula <FORM:0754679/IV(a)/2> with an alkylene oxide of not more than three carbon atoms in the presence of a strong acid catalyst whereby an N-hydroxyalkyl-tert.-carbinamine is formed and in the case of reacting tert.-octyl- and tert.-nonylamines some di-(hydroxyethyl)-tert.-alkylamine may also be formed, destroying this catalyst, removing any water from the amine, and reacting it with an alkylene oxide of not more than 3 carbon atoms under the influence of a strong inorganic base as a catalyst until 3 to 100 mols. of a said alkylene oxide are taken up per mol. of amine, As acid catalysts may be used hydrochloric, hydrobromic, hydriodic, sulphuric, arylsulphonic, alkanesulphonic, nitric, phosphoric or polyphosphoric acids, or the hydrogen form of sulphonated cation-exchange resins.  Equivalent to the use of a hydrohalide is the use of ethylene chlorohydrin or bromohydrin which act as a source both of acid and ethylene oxide.  When one (or, in some cases, two) molecules per molecule of amine have been reacted, the catalyst is destroyed by adding a base, salt and/or water are removed, 0.5 to 5 mol. per cent of an alkaline catalyst is added and ethylene and/or propylene oxides are then run into the mixture.  Suitable catalysts are alkali metal hydroxides, alkali metals, or alkali metal alcoholates.  Suitable carbinamines are 2-amino-2,4,4-trimethylpentane, iso C8H17(C2H5)2CNH2, and narrow mixtures of tert.-alkyl primary amines, e.g. C12H25NH2 to C15H31NH2 and C18H37NH2 to C24H49NH2.  In examples (1) technical tert. octadecylamine (with minor amount of higher tert.-alkyl primary amines) is reacted in the presence of hydrochloric acid with ethylene oxide, and the N-hydroxyethyl-tert.-octadecylamine, after the removal of the catalyst and washing, is reacted in the presence of potassium hydroxide with 10 molecular equivalents of ethylene oxide; (2) a mixture of tert.-carbinylamines from C18 to C24 is reacted as in (1) with a molecular proportion of ethylene oxide. Portions of the recovered product are then reacted with 5, 10, 20 and 50 molecular proportions, respectively, of ethylene oxide; (3) N-hydroxyethyl-tert.-carbinylamine (from the reaction of a tert.-carbinylamine containing mainly a tert.-dodecyl group, with some higher groups up to tert.-pentadecyl) is reacted with 10 molecular proportions of ethylene oxide; (4) tert.-nonylamine (derived from a propylene trimer) is reacted in acid medium with ethylene oxide, and the recovered N-hydroxyethyl-tert.-nonylamine obtained is then reacted in alkaline medium, with either 10 molecular proportions of ethylene oxide or 20 molecular proportions of a 50 : 50 mixture of ethylene and propylene oxides; similar products containing 4 to 50 ethylene oxide residues can be prepared; (5) tert.-octylamine is reacted under acid conditions with ethylene oxide to give N-mono- and di(hydroxyethyl)-tert.-nonylamines which are separated by distillation and reacted with 50 and about 45 molecular proportions of ethylene oxide.  Alternatively, the mixed mono- and di-hydroxy compounds can be reacted with ethylene oxide.  The products have surface-active properties.  They also have anti-corrosive properties, and mixed with the initial carbinamines inhibit the corrosive action of strong acids on metals.