Patented Mar. 18, 1952 2,589,245 UNITED STATES PATENT OFFICE 2,589,245 AMIDE-EPOXIDE COMPOSITIONS, ETC. Sylvan Owen Greenlee, Louisville, Ky., assignor to Devoe & Raynolds Company, Inc., Louisville, Ky., a corporation of New York No Drawing. Application December 3, 1945, Serial No. 632,595 Claims. (Cl. 260-47) 1. 2 This invention relates to new complex amide Another object of the invention is the produc epoxide compositions, and more particularly to tion of Compositions and reaction products of Such compositions capable of conversion into in complex epoxides with amides and amino-amides Soluble, infusible products, and valuable for use of higher unsaturated fatty acids. in making varnishes and protective coatings, in Another object of the invention is the produc making molding compositions and articles, as ad tion of Solutions of such amide-epoxy composi hesives, and in making films and fibres, etc. The tions for use in making warnishes and protective invention includes various new amide-epoxy com coatings, impregnating solutions, films, filaments, positions and reaction products and articles and etc. products made therefrom. 10 Another object of the invention is the produc The new amide-epoxy compositions and prod tion of molding mixtures and compositions ucts are made by reacting amides with complex capable of conversion into infusible, molded ar epoxides produced by the reaction of polyhydric ticles and products, and the articles and prod phenols with polyfunctional halohydrins or with lucts So produced. polyepoxides to form complex reaction products 5 Other objects of the invention and the nature containing terminal epoxide groups. Such epox and advantages of the invention will further ap ide products with which the amides are reacted pear from the following more detailed descrip are advantageously complex polymeric products tion. resulting from the reaction of polyhydric phe In my companion application Serial No. nois with polyfunctional halohydrins or poly 20 617,176, I have described complex, polymeric re epoxides in proportions to give terminal epoxide action products of polyhydric phenols with poly groups in the polymeric reaction products. Such functional halohydrins such as epichlorhydrin Complex epoxide products and compositions are and glycerol dichlorhydrin, with the difunctional described in my companion applications Serial chlorhydrin used in proportions in excess of that Nos. 617,176, 621,856, both now abandoned, and 25 equivalent to the polyhydric phenol and less than 626,449. twice the equivalent amount, by carrying out the One of the objects of the present invention is reaction. With the addition of caustic alkali equal the production of infusible and insoluble reaction to or Somewhat in excess of the amount required products of complex epoxides and amides in suit to combine with the halogen of the halohydrin able proportions which have remarkable chemical and giving complex, polymeric products contain resistance combined with hardness, toughness, 30 ing both terminal epoxy groups and terminal pri flexibility, lack of contraction on conversion, and mary hydroxyl groups, and With the epoxy groups other desirable properties. in general considerably in excess of the terminal Another object of the invention is the produc primary hydroxy groups. Such complex, poly tion of amide-epoxide compositions capable of 35 meric epoxy-hydroxy products and compositions use as raw materials for the production of such are advantageously used for reaction with amides conversion products. to form the new amide epoxy compositions and Another object of the invention is the produc products of the present invention. tion of amide-epoxide compositions which on In my companion application Serial No. conversion result in cross-linking of the complex 621,856, I have described epoxy-hydroxy compo epoxides through reaction of active hydrogens 40 Sitions resulting from the reaction of a polyhy of amides with epoxide groups. dric phenol with a polyfunctional halohydrin Another object of the invention is the produc Such as epichlorhydrin in approximate propor : tion of fusible amide-epoxy compositions and re tions of 2 mols of epichlorhydrin to one of dihy raction products useful for various purposes and dric phenol to give resinous products containing still containing epoxy groups capable of further 45 both terminal epoxy and hydroxy groups with the reaction. proportion of terminal epoxy groups considerably Another object of the invention is the produc in excess of the terminal hydroxy groups. Such tion of compositions and reaction products of epoxy-hydroxy compositions are also advantage polyepoxides With amides in proportions giving Ously used in forming the new amide-epoxy com final infusible products of remarkable chemical 50 positions and products of the present invention. resistivity and other desirable properties. In my companion application Serial No. Another object of the invention is the produc 626,449, I have described new polyepoxy products tion of compositions and reaction products of and compositions obtained by the direct addition complex epoxides with amino-amides containing is of polyhydric phenols with polyepoxides and with both amide and amine groups. the proportion of polyepoxides reacting with the O 2,589,245 3 4. polyhydric phenols in excess of the equivalent and illustrated in the examples are monocarboxyl amount so that the resulting reaction products acid amides of ammonia, or of an aliphatic poly will contain terminal epoxy groups. Such poly amine having two primary groups (Examples epoxy reaction products, and particularly com XVII to XX, XXII, XXIII, XXVI, and XXVIII) plex, polymeric, polyepoxy reaction products, are 5 or polycarboxyl acid amides having hydrogen advantageously used in making the new amide linked directly to the nitrogen of the amide epoxy compositions and products of the present groups (Examples XXI, XXIV, XXV and invention. Such complex epoxides are polymeric XXVII). polyethers of polyhydric phenols and particu Fusible amide-epoxy reaction products can be larly of dihydric phenois having alternating phe prepared with monofunctional amides or with nol residues and aliphatic groups, including hy limited amounts of polyfunctional amides under droxyl-containing intermediate aliphatic groupS proper reaction conditions. The maximum Com and epoxide-containing terminal aliphatic groups plexity of amide-epoxy reaction products appears and in general are free from functional groupS to be obtained when polyfunctional amides, such other than hydroxyl and epoxide groupS. as primary amides and polyamides, are used with Warious amides, and particularly primary car the complex epoxides in proportions close to the boxylic acids amides and polyfunctional car equivalent amounts. Complexity of the products boxylic acids amides, are useful in making the appears to decrease as more or less than the new amide epoxy compositions and products. equivalent amounts of amides are used but infusi Apparently all hydrogens directly attached to ble products can nevertheless be obtained with nitrogen are active hydrogens in reacting with more or less than the equivalent amount of the epoxide groups. The polyamides are more active amides in many cases. Thus with Some of the with the epoxide groups than are the mono amides, particularly polyamides, it is possible to amides and in many cases no catalyst is required obtain infusible products with considerably less to promote reaction of the epoxides with the poly 25 than equivalent amounts of the amides, as well amides. With most amides, especially the mono aS With more than the equivalent amount, prob amides, it is advantageous to use a catalyst, par ably due to the fact that the complex epoxides ticularly if high molecular weight infusible prod are relatively high in molecular weight and the ucts are desired. Alkaline and Friedel-Crafts amount of coupling necessary to make them in type catalyst have been found to be especially fusible is relatively small. active in promoting the reaction of the epoxide The complexity of the final products may also groups with amides. be controlled to some extent otherwise than by In general, carboxylic acids amides containing adjusting the ratio of amide and epoxy reactants, at least two active hydrogens per molecule which as by using moderate reaction conditions such as are directly attached to nitrogen are satisfac 35 lower temperatures or shorter reaction periods tory materials, when used in suitable proportion, Or by using no catalyst, to give fusible products for preparing infusible products in the practice which are valuable intermediate products and of the invention. Amides containing one hydro which may, if the amide and epoxide are only gen per molecule which is directly attached to partially reacted and are in proper proportions nitrogen are in general Satisfactory for prepar 40 for further reaction, give infusible products when ing fusible amide-epoxy products and composi Subjected to such further reaction or conversion. tions While amides containing more than one ac The complex epoxide compositions used with tive hydrogen per molecule directly attached to the amides are themselves capable of polymer nitrogen can be used to form fusible amide-ep ization by reaction of epoxy groups with hydroxyl Oxide compositions and reaction products if used 45 groups, particularly in the presence of. Small in limited amounts. amounts of a catalyst. The complex epoxy com Polyamides are particularly advantageous. positions made from polyhydric