Patent GB-887589-A (GB)
Title: New nitrogenous epoxide compounds and process for their manufacture
Filed: 1959-03-26
Abstract: Hardenable compositions comprise a nitrogenous epoxide compound of formula <FORM:0887589/IV (a)/1> where the "R" groups each represent hydrogen or an aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon radical or R1 and R5 and/or R11 and R51 together represent a methylene group, X and Y each represent an acyl, carbalkoxy, carbaryloxy, cyano or sulphonyl-containing group (specifically sulphonic acid or ester or the acid radical of a sulphonic acid), Z represents a divalent hydrocarbon radical which may be interrupted by heteroatoms such as nitrogen, oxygen or sulphur or by sulphone groups, and n is 1 or 2, and a hardening agent for epoxide resins.  Specified hardening agents include amines (including triethanolamine), amides, guanidines, Mannich's bases, aminoplasts, polyamides, poly(amino-styrenes), isocyanates, isothiocyanates, polyphenols, phenolaldehyde resins, aluminium alcoholate or phenolate/keto-enol compound reaction products, Friedel-Crafts catalysts, phosphoric acids and polycarboxylic acids and their anhydrides.  An accelerator such as a tertiary amine, specifically bis-(D 3-tetrahydrobenzyl)-methylamine, may be present. Fillers, e.g. asphalt, bitumen, glass fibres, mica, quartz, cellulose, kaolin and silicic acid, plasticizers, colouring matter and the like may be present.  Cast resins are prepared in examples from: (1) N,N-bis-(3,4-epoxyhexahydrobenzyl)-formamide and methylendomethylene-tetrahydrophthalic anhydride; (2) N,N-bis-(3,4 - epoxyhexahydrobenzyl) - acetamide and phthalic anhydride; (3) N,N-bis-(3,4-epoxyhexahydrobenzyl)-p-toluene-sulphonamide and phthalic anhydride; (6) N,N1-diacetyl -N,N1-bis-(3,4 -epoxyhexahydrobenzyl)-ethylene diamine, bis-D 3-tetrahydrobenzyl methylamine and phthalic anhydride; (7) N,N1-diacetyl -N,N1-bis-(3,4 -epoxyhexahydrobenzyl) - hexamethylenediamine and methylendomethylene-tetrahydrophthalic anhydride and (11) N,N-bis-(3,4-epoxyhexahydrobenzyl)-acetamide and BF3/ethylamine complex, which is compared with a resin derived from 6,61-dimethyl - 3,4 - epoxy - hexahydrobenzyl - 31,41 - epoxyhexahydrobenzoate and the same catalyst.  Uses are said to include textile assistants, laminating resins, lacquers, paints, dipping resins, cast bodies, spreadable or putty-like masses, moulding compositions and adhesives.ALSO:The invention comprises nitrogenous epoxide compounds of formula (I) <FORM:0887589/IV (b)/1> where the "R" groups each represent an aliphatic, cycloaliphatic, araliphatic or aromatic hydrocarbon radical or a hydrogen atom, or R1 and R5 and/or R11 and R15 together represent a methylene group, X and Y each represent an acyl, carbalkoxy, carbaryloxy, cyano or sulphonylcontaining group (specifically sulphonic acid or ester or the acid radical of a sulphonic acid), Z represents a divalent hydrocarbon radical which may be interrupted by heteroatoms, such as nitrogen, oxygen or sulphur, or by sulphone groups and n is 1 or 2.  They are prepared by reacting the corresponding cyclohexene compounds (II) <FORM:0887589/IV (b)/2> with an epoxidising agent such as peracetic or perbenzoic acid.  The cyclohexene compounds (II) are obtained by reacting the corresponding secondary amines in which X and Y are hydrogen with agents capable of introducing an acyl, carbalkoxy, carbaryloxy, cyano or sulphonyl-containing group.  The secondary amines of formula (III) <FORM:0887589/IV (b)/3> may be obtained by reducing a compound <FORM:0887589/IV (b)/4> where B is -CN, -CONH2, -CH=NH, -CH=N-OH, or a Schiff's base in which B is <FORM:0887589/IV (b)/5> or the components forming it, under conditions which do not saturate the olefinic link, e.g. sodium in an alcohol medium, lithium aluminium hydride or, for certain compounds such as cyclohexane nitrile, catalytic hydrogenation, e.g. using Raney nickel or copper chromite catalyst.  Secondary diamines of formula <FORM:0887589/IV (b)/6> are prepared by reducing a Schiff's base of formula <FORM:0887589/IV (b)/7> or <FORM:0887589/IV (b)/8> as above.  The various types of Schiff's base are prepared by condensing appropriate aldehydes and amines.  Bis-(D -tetrahydrobenzyl)-methylamine is prepared by treating bis-(D 3-tetrahydrobenzyl)-amine with formaldehyde in the presence of formic acid.