Patent GB-818844-A (GB)
Title: New hardenable derivatives of formaldehyde condensation products of the aminotriazine or urea group, and their manufacture and use
IPC: C08G12/40
Filed: 1955-08-24
Abstract: The invention comprises hardenable cationactive derivatives of formaldehyde condensation products of compounds of the urea or aminotriazine series or ethers thereof with C1-C4 alcohols, which derivatives have (1) at least one free or etherified methylol group, (2) a polyglycol chain or a plurality of hydroxyethyl groups, (3) basic nitrogen atoms, and (4) no epoxide group.  The components for making the derivatives are (a) a formaldehyde condensation product of a compound of the urea or aminotriazine series or an ether thereof with a C1-C4 alcohol, or a derivative (e.g. ester or ether) containing a hydrocarbon radical of 7 or more carbon atoms (such product having at least two methylol groups, free or etherified); (b) a compound capable of introducing a polyglycol ether chain or a plurality of hydroxyethyl groups; and (c) a primary, secondary or tertiary amine or salt or quaternary derivative thereof; the product is converted into a water-soluble or quaternary derivative if not such already.  The starting materials can comprise mixtures, and can be reacted together simultaneously or in stages in any order.  It is preferred either to react (b) with (c) and then the product with (a), or to react (a) with part of (b), (c) with the rest of (b) and then the two condensation products together.  If any starting material contains an epoxide group this is opened during the reaction by choosing appropriate reaction conditions.  Component (a) can be a methylol derivative of melamine, melam, melem, ammeline, ammelide, halo-aminotriazines, guanamines, guanyl-melamines (see Specification 730,018), urea, thiourea, dicyandiamide, dicyandiamidine, guanidine, acetoguanidine or biguanide; an ether of the preceding with a C1-C4 alcohol; a partial ether of any of the preceding with a higher alkanol, alkenol or benzyl alcohol; a partial ester of any of the preceding with a higher alkanoic, alkenoic, cycloaliphatic or aromatic acid; an amide derivative analogous to the above esters; or a partially polymerized or condensed derivative of the above. Component (b) can be ethylene oxide or a polyglycol or ether or ester thereof, e.g. a methyl ether, a glyceryl ether or an acetate. Component (c) can be an alkylamine, alkanolamine, alkylene diamine or polyalkylene polyamine, especially one containing an alkyl, alkenyl or cycloalkyl group of 8-40 carbon atoms attached directly or via an ester, ether or amide group; a cycloalkylamine or aralkylamine; an amino-substituted aromatic or heterocyclic compound; a compound containing an N-atom in a ring.  Many suitable compounds of the above types are mentioned (e.g. dimethylethanolamine).  The quaternating agent used before or after the condensation may be e.g. dimethyl sulphate, benzyl chloride, chloroacetamide or Nmethylol-chloroacetamide.  The relative proportions of the components depend on the number of methylol groups in component (a) and the extent of any higher hydrocarbon groups present.  The reaction may be carried out wholly or in part on a substratum such as a textile fibre.  In examples: (1) hexamethylol-melamine is reacted successively with methyl alcohol (to etherify all the hydroxyl groups), 3 mols. of Nmethylol-chloracetamide and 1.5 mols. of the product of reacting 15 mols. of ethylene oxide with 1 mol. of N-(tallow alkyl)-trimethylene-diamine; (2) as in (1) but reacting the hexa(methoxy-methyl)-melamine with 2 mols. of polyethylene glycol before the amide and using only 1 mol. of the last component; (2) the following are reacted in the order stated: diethylene triamine, ethylene oxide, N-methylol-stearamide, hexa-(methoxymethyl)-melamine, benzyl chloride; (4) the following are reacted in order: N-(tallow alkyl)-trimethylene diamine, ethylene oxide, hexa - (methoxymethyl) - melamine, dimethyl sulphate; (5) the following are reacted in order: diethylene triamine, stearic acid, ethylene oxide, hexa-(methoxymethyl)melamine, acetic acid; (6) the condensation product of triethanolamine and ethylene oxide is reacted with urea and formaldehyde, and acidified with hydrochloric acid.  Compounds analogous to those of the present invention but without the residue of component (b) are described in Specification 779,232.ALSO:The invention comprises hardenable cationactive derivatives of formaldehyde condensation products of compounds of the urea or aminotriazine series or ethers thereof with C1-C4 alcohols, which derivatives have (1) at least one free or etherified methylol group, (2) a polyglycol chain or a plurality of hydroxyethyl groups, (3) basic nitrogen atoms, and (4) no epoxide group.  The components for making the derivatives are (a) a formaldehyde condensation product of a compound of the urea or aminotriazine series or an ether thereof with a C1-C4 alcohol, or a derivative (e.g. ester or ether) containing a hydrocarbon radical of 7 or more carbon atoms (such product having at least two methylol groups, free or etherified); (b) a compound capable of introducing a polyglycol ether chain or a plurality of hydroxyethyl groups; and (c) a primary, secondary or tertiary amine or salt or quaternary derivative thereof; the product is converted into a water-soluble or quaternary derivative if not such already.  The starting materials can comprise mixtures, and can be reacted together simultaneously or in stages in any order. It is preferred either to react (b) with (c) and then the product with (a), or to react (a) with part of (b), (c) with the rest of (b) and then the two condensation products together.  If any starting material contains an epoxide group this is opened during the reaction by choosing appropriate reaction conditions. Component (a) can be a methylol derivative of melamine, melam, melem, ammeline, ammelide, halo-aminotriazines, guanamines, guanyl-melamines (see Specification 730,018), urea, thiourea, dicyandiamide, dicyandiamidine, guanidine, acetoguanidine or biguanide; an ether of the preceding with a C1-C4 alcohol; a partial ether of any of the preceding with a higher alkanol, alkenol or benzyl alcohol; a partial ester of any of the preceding with a higher alkanoic, alkenoic, cycloaliphatic or aromatic acid; an amide derivative analogous to the above esters; or a partially polymerized or condensed derivative of the above. Component (b) can be ethylene oxide or a polyglycol or ether or ester thereof, e.g. a methyl ether, a glyceryl ether or an acetate. Component (c) can be an alkylamine, alkanolamine, alkylene diamine or polyalkylene polyamine, especially one containing an alkyl, alkenyl or cycloalkyl group of 8-40 carbon atoms attached directly or via an ester, ether or amide group; a cycloalkylamine or aralkylamine; an amino-substituted aromatic or heterocyclic compound; a compound containing an N-atom in a ring. Many suitable compounds of the above types are mentioned (e.g. dimethylethanolamine).  The quaternating agent used before or after the condensation may be e.g. dimethyl sulphate, benzyl chloride, chloracetamide or N-methylol-chloracetamide.  The relative proportions of the components depend on the number of methylol groups in component (a) and the extent of any higher hydrocarbon groups present.  The reaction may be carried out wholly or in part on a substratum such as a textile fibre.  In examples: (1) hexamethylol-melamine is reacted successively with methyl alcohol (to etherify all the hydroxyl groups), 3 mols. of N-methylol-chloracetamide and 1.5 mols. of the product of reacting 15 mols. of ethylene oxide with 1 mol. of N-(tallow alkyl)-trimethylenediamine; (2) as in (1) but reacting the hexa-(methoxymethyl)-melamine with 2 mols. of polyethylene glycol before the amide and using only 1 mol. of the last component; (3) the following are reacted in the order stated: diethylene triamine, ethylene oxide, N-methylolstearamide, hexa - (methoxymethyl) - melamine, benzyl chloride; (4) the following are reacted in order: N-(tallow alkyl)-trimethylene diamine, ethylene oxide, hexa-(methoxymethyl)-melamine, dimethyl sulphate; (5) the following are reacted in order: diethylene triamine, stearic acid, ethylene oxide, hexa-(methoxymethyl)-melamine, acetic acid; (6) the condensation product of triethanolamine and ethylene oxide is reacted with urea and formaldehyde, and acidified with hydrochloric acid. Compounds analogous to those of the present invention but without the residue of component (b) are described in Specification 779,232.ALSO:The surface conductivity of textile materials is improved by treating them with a compound as defined below, or with the components for making such a compound, the reaction being then completed on the fibre.  The materials are impregnated with an aqueous or organic solution of the compound, dried, and, if desired, heated to, e.g., 120-150 DEG  C., preferably in the presence of a hardening catalyst such as an acid or a salt thereof with a weak base.  If an organic solvent is used this can be the acid or an ester which generates it on heating.  If the compound contains a polymerizable group, this can be polymerized on the fibre in the presence of a catalyst such as a peroxide or per-salt, as in the process of Specification 779,232.  The compounds of the invention are hardenable cation-active derivatives of formaldehyde condensation products of compounds of the urea or triazine series of ethers thereof with C1-C4 alcohols, which derivatives have (1) at least one free or etherified methylol group, (2) a polyglycol chain or a plurality of hydroxyethyl groups, (3) basic nitrogen atoms, and (4) no epoxide group.  The components for making the compounds are: (a) a di- or poly-methylol derivative of melamine, melam, melem, ammeline, ammelide, halo - aminotriazine, guanamine, guanyl - melamine (see Specification 730,018), urea, thiourea, dicyandiamide, dicyandiamidine, guanidine, acetoguanidine or biguanide; an ether of the preceding with a C1-C4 alcohol; a partial ether of