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United States Patent Office Patented Oct 3,404,128 United States Patent Office Patented Oct. 1, 1968 1. 2 phenolic acid which comprises a mixture of the mono 3,404,128 amino amide and diamide wherein the mono-amide is METHOD FOR PREPARING A DIPHENOLIC ACID. AMIDE PHENOL-ALDEHYDE RESIN Substantially prevailing. It has been found that it is par Sol B. Radlove, Abraham Ravve, and Chester W. Fitko, tially the unreacted primary amine groups of the mono Chicago, Ill., assignors to Continental Can Company, 5 amides which are subsequently reacted in the condensa Inc., New York, N.Y., a corporation of New York tion of the polyfunctional phenol and formaldehyde No Drawing. Filled June 4, 1965, Ser. No. 461,546 which bond the diphenolic acid amides to the thermo 11 Claims. (Cl. 260-51.5) Setting resin and thus provide a continuous adherent coat ing which is highly flexible and substantially resistant to chemicals. The diphenolic acid mono- and di-amides are ABSTRACT OF THE DISCLOSURE 10 sufficiently bonded to the phenolic-resin system so as to A diphenolic acid coating resin is prepared by reacting result in a homogeneous composition which is uniform a diphenolic acid amino amide with a polyfunctional throughout and can be used effectively for preparing phenol and formaldehyde, the diphenolic acid amino thermosetting films. amide being prepared by the reaction of a polyamine and One of the essential elements of this invention is that a diphenolic acid, the polyamine being present in excess it is necessary to prepare the amide from polyamines of the stoichiometric amount required to react with the and diphenolic acids wherein the polyamine contains two diphenolic acid. A thermosetting polymeric coating com primary amine groups, one of which remains unreacted position is prepared by reacting the diphenolic acid coat after the amidification and is available to react in the 20 Subsequent condensation with the phenol and formalde ing resin with an epoxy resin. hyde. The unreacted or unbound primary amino group imm of the mono-amide is obtained in relative large propor This invention is directed to a method of preparing a tions by utilizing in excess of the polyamine which must polymeric coating composition and more specifically to contain two primary amine groups. The excess ranges a method of preparing a diphenolic acid coating resin 25 from about 5-100% over the stoichiometric amount re and to its use in combination with an epoxy resin as a quired to form the diamide. coating composition for various substrates, such as metal. The diphenolic resins which are obtained from the Still more specifically, this invention is directed to a reaction of these diphenolic acid amides with phenol and composition comprising diphenolic acid resins in com formaldehyde may be used in combination with an epoxy bination with epoxy resins and to the method of using 30 resin to obtain coatings which are substantially superior these compositions for preparing thermosetting coatings to similarly known coating compositions. The coatings on metal surfaces. The diphenolic acid resins, as prepared prepared in accordance with the teachings of this inven in accordance with this invention, can be used either tion have outstanding physical and chemical properties alone or in combination with known epoxy resins, and and have demonstrated that the resin forms tough, flexi have been found to be particularly useful for the forma ble films which are highly resistant to oxidation, acids, tion of coatings on metal surfaces, such as the interior of alkali constituents and various other organic solvents. cans. Coating compositions containing the diphenolic acid These coatings are highly adherent to various surfaces, resins of this invention have been found to provide a including metal, plastics, etc. and, therefore, can be used flexible, adherent film on metal surfaces and are partic for forming films on articles which require a high degree ularly outstanding with respect to their resistance to 40 of flexibility and outstanding chemical resistance. chemicals. Accordingly, it is an object of this invention to pro Heretofore, attempts to use diphenolic acid compounds, vide a method of preparing a diphenolic resin containing and more particularly the diamides of diphenolic acid, mono-and diamides of a diphenolic acid. Still further, it for the preparation of good coating compositions, have is an object of this invention to provide a method of not proven to be completely satisfactory. However, these preparing diphenolic resins containing mono-and di diphenolic acid compounds and particularly the poly amides of diphenolic acid reacted with formaldehyde and amides thereof have been utilized for preparing thermo a polyfunctional phenol. Set coatings. More particularly, the use of diphenolic acid It is another object of this invention to provide a terminated polyamides reacted with formaldehyde either method of preparing diphenolic resins containing a mix alone or in combination with phenols may have been 50 ture of mono- and diamides of a diphenolic acid which Suggested as a means of preparing thermosetting coatings. can be used for preparing a thermosteering composition However, in prior compositions the diphenolic acid poly which is highly adherent to various surfaces, particularly amide is a completely amidified product in which there metal, and is substantially resistant to corrosive chemicals. are no free primary amino groups available to react with Still a further object of this invention is to provide a di either the phenol or the aldehyde. Thus, most of these 55 phenolic acid resin composition prepared by condensing compositions form films which are very hard and less a polyfunctional phenol with formaldehyde and a diphe flexible because of the type of cross-linking. nolic acid amide wherein the diphenolic acid amide is To overcome the insufficiencies of coatings of similar prepared by reacting the acid with an excess of a poly compositions known heretofore, it has been found that amine containing two primary amine groups. it is essential to prepare the diphenolic acid amides by 60 It is another object of this invention to provide a com utilizing an excess of the polyamine so as to obtain a position containing a diphenolic resin in combination with product which is a mixture of both the mono-amino an epoxy resin solubilized in inert-volatile organic solvents amide and the diamide of the diphenolic acid. Moreover, which may contain pigments or other known vehicles; the polyamines used in preparing the amides must have Said diphenolic resin being prepared by condensing a poly two primary amine groups and must be used in an 65 functional phenol with mono- and diamides of a diphe amount ranging from about 5-100% and more prefer nolic acid and formaldehyde. ably 40-100% in excess of the theoretical stoichiometric It is still a further object of this invention to pro amount required to form the diamide of the polyamide. vide a method of coating various substrates, including Thus, by utilizing, for example, 100% in excess of the metal, with a thermosetting resin composition which may polyamine normally required to form the diamide of the 70 be cured at temperatures ranging up to about 500 F. polyamine, it is possible to obtain amides of the di It is still a further object of this invention to provide 3 3,404,128 a method of providing a metal substrate containing a highly flexible and have outstanding chemical and physi thermosetting coating composition which comprises a par cal properties. - - - - - ticular diphenolic resin in combination with an epoxy DIPHENOLIC ACID AMIDES cS1. It is still a further object of this invention to provide 5 In preparing the diphenolic acid amides for purposes a method of preparing a continuous, adherent coating of this invention, it is essential that the polyamine have composition which is highly flexible and substantially re two primary amine groups per molecule such that upon sistant to various chemicals and which comprises a combi amidifying the polyamine with the diphenolic acid, at nation of an epoxy resin and a particular diphenolic resing least one of the said primary amine groups remains un the diphenolic resin being prepared by condensing form reacted in the form of a mono-amino amide. The rela aldehyde with a polyfunctional phenol and a diphenolic 10 tive proportion of the mono-amino amide with the di acid amide, said amide being obtained by amidifying a di amide adducts will obviously depend upon the amount of phenolic acid with an excess of a polyamine containing eXcess used in the amidification process. Thus, for ex two primary amine groups. ample, where 100% of an excess of polyamine having It is still a further object of this invention to provide two primary amine groups us used in the amidification of a thermosetting composition and a method of preparing the diphenolic acid, it is possible to obtain a mixture of mono-amino amides and the diamide adducts wherein the same for use as a coating on various metal surfaces mono-amino amide ranges from about 70-90% of the which comprises the combination of an epoxy resin and mixture. On the other hand, if only a stoichiometric a diphenolic resin; the diphenolic resin being prepared amount of a polyamine is used in the amidification process, by condensing a phenol with formaldehyde and a diphe 20 all of the primary amino groups would be completely re nolic acid mono- and diamide. acted, thus leaving no free or unbound primary amine These and other objects of the invention will become groups for the Subsequent reaction with the phenol and apparent from a further and more detailed discussion of formaldehyde. the invention. A number of polyamines which have two primary More specifically, it has been discovered, quite unex amine groups may be used and include such compounds pectedly, that continuous-adherent thermosetting coating as ethylene diamine, diethylene triamine, triethylene films can be obtained by utilizing a particular diphenolic tetramine, tetraethylene pentamine, 1,3 - diamino pro resin in combination with an epoxy resin solubilized in pane, imino - bis - propyl amine, N,N- bis (3 - amino inert volatile organic solvents.
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