Patent GB-864699-A (GB)
Title: New ethers containing epoxide groups
IPC: C07D405/12
Filed: 1958-07-16
Abstract: Epoxy resin compositions comprise ethers of N-methylolamino-1 : 3 : 5-triazines in which at least one N-methylol group is etherified with a residue containing an epoxide group and hardeners.  Preferred ethers correspond to the formula:-  <FORM:0864699/IV (a)/1> in which R1, R2 and R3 each represent a hy drogen atom or an alkyl or alkenyl radical containing 1 to 4 carbon atoms or a glycidyl resdue; x1, x2 and x3 each is 1 or 2; and A stan for an aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon residue or a residue of the formula:-  <FORM:0864699/IV (a)/2> in which R4 and R5 respectively have the same meanings as R1, R2 and R3, and x4 and x5 have the same meanings as x1, x2 and x3, or A represents a second etherified methylolamino1 : 3 : 5-triazine residue joined to the first by an alkylene radical of up to 4 carbon atoms.  Suitable hardeners include mono-, di- or tri-butylamines, p-phenylenediamine, ethylenediamine, N; N-diethyl-ethylenediamine, diethylenetriamines triethylenetetramine (Example 8), trimethylamine, diethylamine, triethanolamine, Mannich bases, piperidine, piperazine, guanidine, phenyl-guanidine, diphenylguanidine, dicyandiamide, aniline-formaldehyde resins, polymers of aminostyrenes, polyamides from aliphatic polyamines and dimerized or trimerized unsaturated fatty acids (Example 9), isocyanates, isothiocyanates, polybasic carboxylic acids and anhydrides thereof, such as phthalic anhydride, methylendomethylenetetrahydrophthalic anhydride (Example 11), endomethylenetetrahydrophthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, hexachloroendomethylenetetrahydrophthalic anhydride (Example 11) or mixtures thereof (Example 11); maleic or succinic anhydride, resorcinol, hydroquinone, quinone, phenol-aldehyde resins, oilmodified phenol aldehyde resins, reaction products of aluminium alcoholates or phenolates with tautomeric compounds such as acetoacetic ester, Friedel Crafts catalysts, e.g. AlCl3, SbCl3, SnCl4, FeCl3, ZnCl2, BF3 and their organic complexes, and particularly phosphoric acid (Example 10).  Fillers such as glass fibres, mica, quartz powder, cellulose, kaolin, silicic acid or metal powders may also be present.  The mixtures of polyglycidyl ethers and hardeners can be used with or without a filler for the manufacture of laminating resins, lacquer coatcoatings, casting resins, pore fillers, putties and adhesives.  When phosphoric acid is used, the product is suitable for cementing glass.  Specification 801,728 is referred to.ALSO:The invention comprises ethers of N-methylolamino- 1:3:5-triazines in which there is at least one N-methylol group with a residue containing an epoxide group, preferably a glycidyl residue. Preferred ethers correspond to the formula:  <FORM:0864699/IV (b)/1> in which R1, R2 and R3 each represent a hydrogen atom, or an alkyl or alkenyl radical containing 1 to 4 carbon atoms or a glycidyl residue; x1 x2 and x3 each is 1 or 2; and A represents an aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon residue, or a residue of the formula:  <FORM:0864699/IV (b)/2> in which R4 or R5 respectively have the same meanings as R1, R2 or R3 and x4 and x5 have the same meanings as x1, x2 and x3.  A may also represent a second etherified methylolamino- 1:3:5-triazine residue joined to the first by an alkylene radical of up to 4 carbon atoms.  The new compounds may be obtained by reacting an N-methylolamino- 1:3:5-triazine, or an ether thereof derived from an alcohol containing 1 to 4 carbon atoms, with a halogenohydrin derived from a polyhydric aliphatic alcohol containing at least 3 carbon atoms, said halogenohydrin containing in addition to the hydroxyl group vicinal to the halogen atom at least one additional etherifiable, alcoholic hydroxyl group, the resulting etherification product containing halogenhydrin groups then being converted into the corresponding epoxy compound in the presence of an alkali.  Starting materials include trimethylolmelamine, hexamethylolmelamine, and methylol compounds of N-substituted melamines, melam, melem, ammeline, ammelide, halogen-substituted-aminotriazines, guanamines and diguanamines, or ethers thereof.  The reaction of this starting material with the halogenohydrin is preferably effected in neutral or acid medium, with heating to 70-100 DEG C.  The conversion to the epoxide is preferably effected with strong alkalies, if desired, in an inert organic solvent.  The products may be cross-linked and hardened like other epoxy resins.  Specification 801,728 is referred to.