Patent GB-1014884-A (GB)
Title: Epoxy resins and utilization thereof
IPC: D21H17/54
Filed: 1962-07-30
Abstract: Hydrophilic, thermoplastic resins which are soluble in a 2.5% by wt. hydrochlorine acid solution are prepared by reacting an epoxide with a polyamine containing more than two carbon atoms and at least two amino groups, each having at least one hydrogen atom attached to nitrogen, but not more than two primary amino groups; and reacting the product with an epoxide or with a compound which introduces an epoxy group into the molecule under conditions to avoid gel formation.  Suitable epoxide starting materials are the diglycidyl ether of 4,41-dihydroxydiphenyldimethylenethane; butadiene diepoxide; compounds of formula <FORM:1014884/C3/1> or of formula <FORM:1014884/C3/2> or allyl glycidyl ether.  Suitable amines are 1,3-propylene diamine N-methyl-1,2-propylene diamine, N-propyl propylene diamine, butylene-1,2-diamine, hexamethylene diamine, diethylene triamine, triethylene tetramine, tetraethylenepentamine, di-1,2-propylenetriamine.  In examples resins are prepared from I. The reaction product of EPON 828 with diethylene triamine was reacted with further EPON 828. The second reaction was stopped at incipient gelation by acidification.  II (a) Hexamethylene diamine was reacted with two lots of EPON 828. (b) Triethylene tetramine was similarly reacted. III Tetraethylene pentamine was reacted with two lots of (a) butadiene dioxide; (b) EPON 812; and (c) resorcinol diglycidyl ether. IV Tetraethylene pentamine was reacted with EPON 828 and the product with epichlorohydrin. V Tetraethylene pentamine was reacted with two lots of EPON 828.  If desired the epoxidized products of the invention may be reacted with formaldehyde to increase their reactivity (see Examples VI-IX). Ethylenically unsaturated groups may be introduced into the epoxides of the invention to permit copolymerization with for example, acrylonitrile, styrene, vinyl toluene, acrylic acid, and methyl or ethyl methacrylates.  In Example X, allyl glycidyl ether is reacted with tetraethylene pentamine and the product reacted with EPON 828, and in Example XI, the product of Example X was reacted with formaldehyde.  The epoxy-containing products of the invention may also be reacted with long chain fatty amines, e.g. dodecylamine, tetradecylamine hexadecylamine oleylamine, or N - alkyl-trimethylene diamines prepared by reacting long chain fatty amines with acrylonitrile and then hydrogenating.  In Example XII an N-alkyl trimethylene diamine known as Duomeen O, and tetraethylene pentamine were reacted with EPON 828 in two stages.  In Example XIII the product of Example XII was reacted with formaldehyde.  Example XIV reacts tetraethylene pentamine and dodecylamine with two lots of EPON 828, and the product was reacted in Example XV with formaldehyde.  The products of the invention on cationic water-soluble resins useful for treating anionic fibres, e.g. cellulose in the manufacture of paper, wall board and other fibrous articles. They are usually aqueous solutions but may be dissolved in organic solvents.  Some of the products are useful sizing agents for glass fibre in polyester mouldings.  They may also be used to modify starch products.  In Example XXIII potato starch was stirred into water and a resin prepared from diethylene triamine reacted in two stages with EPON 828 to yield a cationic starch which can be transformed into a white opaque gel by addition of a water-soluble phenolic resin.ALSO:Anionic fibres, e.g. cellulose are treated with thermoplastic cationic resins which are soluble in dil HCl and are prepared by reacting an epoxide with a polyamine, and introducing epoxy groups into the product by reaction to the point of incipient gelation with an epoxide.  The fibres are used for making paper, mouldings, wallboard or other fibrous articles.  If desired the resins may be rendered non active by reaction with formaldehyde. In Example XVI paper was prepared from cellulose fibre treated with a resin derived from di-ethylene triamine by a treatment in two stages with an epoxide known as EPON 828.  In Example XVII sisal fibres treated with the same resin are used, either alone or mixed with unmodified sisal fibres.  The treated fibres are oil-wetting.  In Example XVII, the resin is applied to paper as a tub size.  Cellulon treated according to the invention has the ability to bond or adhere to materials such as polystyrene, petroleum resins, oleoresinous varnishes, and polyester resins.  In Example XIX cellulose was treated with a resin from tetraethylene pentamine treated with two successive lots of EPON 828, both alone and with formaldehyde, and a phenolic resin known as Resinon 594 was used as a beater addition to the modified cellulose a production of paper.  Examples XX to XXII describe similar treatments of cellulon fibres.