Patent GB-877062-A (GB)
Title: Surface-active basic polyethers
IPC: C23G1/06
Filed: 1959-02-18
Abstract: Water-soluble nitrogenous polyethers, having emulsifying and detergent properties are obtained by etherifying a phenolic amine of formula:  <FORM:0877062/IV (a)/1> (wherein A is an alkyl group containing up to 20 carbon atoms or is a C6-C10 cycloalkyl group and r is 1 or 2, the A group or groups having a total of at least 4 carbon atoms; R is a benzene nucleus; X is hydrogen, a C1-C20 alkyl group, a C6-C10 cycloalkyl group, or a C2-C20 hydroxy alkyl group; Y is a C2-C20 hydroxyalkyl group, and n is 1 or 2) with 8-50 moles of ethylene oxide per mole of the phenolic amine.  The reaction may be carried out at atmospheric or higher pressures, preferably under a blanket of nitrogen, and at raised temperatures, e.g. 90 DEG -150 DEG C., at which temperatures no catalyst is required.  The products are viscous liquids.  When there are two groups A, these may be alike or different.  Phenolic amines having in p-position a tert. octyl, isononyl, isododecyl, or iso-octadecyl group are preferred as starting materials, and preferably the groups X and Y are the same hydroxyalkyl group e.g. 2-hydroxyethyl.  The group X may be 2-ethylhexyl, dodecyl, octadecyl, cyclohexyl, fenchyl, or isobornyl, and in these cases the group Y is preferably 2-hydroxyethyl.  The products obtained are polyethers formed by the addition to the hydroxyl groups present in the starting phenolic amine of at least 8 moles of ethylene oxide per mole of starting material.  The addition may take place mainly on the phenolic or on the alcoholic hydroxyl groups or on both.  Examples of products which may be obtained are indicated by a table of values for A, X, Y, n, and the number of moles of ethylene oxide combined with each mole of the phenolic amine.  In one example, 35 moles of ethylene oxide are combined with each mole of a phenolic amine of the stated general formula in which A is iso-octadecyl, X is cyclohexyl, Y is 2-hydroxyethyl, and n is 1.ALSO:Water-soluble, basic nitrogenous ethers, having emulsifying and detergent properties, are obtained by etherifying a phenolic amine of formula <FORM:0877062/IV (b)/1> (wherein A is an alkyl group containing up to 20 carbon atoms or is a C6-C10 cycloalkyl group and r is 1 or 2, the A group or groups having a total of at least 4 carbon atoms; R is a benzene nucleus; X is hydrogen, a C1-C20 alkyl group, a C6-C10 cycloalkyl group or a C2-C20 hydroxyalkyl group; Y is a C2-C20 hydroxyl-alkyl group, and n is 1 or 2) with 8 to 50 moles of ethylene oxide per mole of the phenolic amine.  The reaction may be carried out at atmospheric or higher pressures and preferably at 90 DEG -150 DEG C., at which temperatures no catalyst is required, and under a blanket of nitrogen.  The products are viscous liquids which may be used directly as detergents.  The group A may be a primary, secondary, or tertiary, alkyl group.  When there are two groups A these may be alike or different.  Phenolic amines having in para-position a tert. octyl, isononyl, isododecyl, or isooctadecyl group are preferred as starting materials, and preferably the groups X and Y are the same hydroxyalkyl group e.g. 2-hydroxyethyl or 2-hydroxypropyl.  The group X may be 2-ethylhexyl, dodecyl, octadecyl, cyclohexyl, fenchyl, or isobornyl, and in these cases the group Y is preferably 2-hydroxyethyl.  When X is hydrogen, or methyl, ethyl, butyl, or amyl, Y is preferably 2-hydroxypropyl, hydroxybutyl, or hydroxyoctyl.  The products obtained are polyethers formed by the addition to the hydroxyl groups present in the starting phenolic amine of at least 8 moles of ethylene oxide per mole of starting material.  The addition may take place mainly on the phenolic or the alcoholic hydroxyl group of the starting material or on both. Examples of products which may be obtained are indicated by a table of values for A, X, Y, n, and the number of moles of ethylene oxide combined with each mole of the phenolic amine.  In one example, 10 moles of ethylene oxide are combined with each mole of a phenolic amine of the stated general formula in which A is isononyl, X and Y ar 2-hydroxyethyl and n is 2.  Other examples indicate a compound in which the benzene nucleus contains an octyl substituent in para position and a methyl group in ortho position, and one in which there is a nonyl group in para position and a tertiary butyl group in ortho position.  The compounds inhibit the corrosion of metals such as iron, steel, and copper, by acids, and they may be used for this purpose in pickling and other acid solutions for treating metals.ALSO:Detergent compositions comprise a water-soluble nitrogenous ether which is obtained by etherifying a phenolic amine of formula <FORM:0877062/III/1> (wherein A is an alkyl group of up to 20 carbon atoms or is a C6-C10 cycloalkyl group and r is 1 or 2, the A groups having a total of at least 4 carbon atoms; R is a benzene nucleus; X is hydrogen, a C1-C20 alkyl group, a C6-C10 cycloalkyl group or a C2-C20 hydroxyalkyl group; Y is a C2-C20 hydroxyalkyl group, and n is 1 or 2) with 8-50 moles of ethylene oxide per mole of the phenolic amine.  The compounds are polyethers formed by addition of ethylene oxide at hydroxyl groups of the starting phenolic amine, the addition taking place mainly on the phenolic or the alcoholic hydroxyl group or on both.  Phenolic amines having in para position a tert. octyl, isononyl, isododecyl, or isooctadecyl group are preferred as starting materials.  The groups X and Y may be the same hydroxyalkyl group, e.g. 2-hydroxyethyl.  The Group X may be 2-ethyl hexyl, dodecyl, cyclohexyl, fenchyl, or isobornyl. These polyethers may be used as household detergents.  For heavy duty detergent purposes, the polyethers of the invention may be used in admixture with non-ionic surface-active agents of the type Alkyl-C6H4-(OCH2.CH2)x.OH wherein the alkyl group contains 8-12 carbon atoms and x is 6-30.  The polyethers of the invention and their aqueous solutions may be stored in tin cans without causing rusting.ALSO:Pickling and other acid solutions for treating metals e.g steel and copper contain as agent for preventing undesired corrosion, a water-soluble, basic, nitrogenous, polyether which is obtained by reacting a phenolic amine of formula <FORM:0877062/II/1> (wherein each A is an alkyl group containing up to 20 carbon atoms or a C6-C10 cycloalkyl group and r is 1 or 2, the A groups containing a total of at least 4 carbon atoms; R is a benzene nucleus; X is hydrogen, a C1-C20 alkyl group, a C6-C10 cycloalkyl group, or a C2-20 hydroxyalkyl group; Y is a C2-C20 hydroxyalkyl group, and n is 1 or 2), with 8-50 moles of ethylene oxide per mole of phenolic amine. The group A may be tert. octyl, or isooctadecyl. The groups X and Y may both be 2-hydroxyethyl.  Group X may be dodecyl, cyclohexyl, fenchyl, or isobornyl.