2,928,811 Patented Mar. 15, 1960 2 2,928,811 Glycidyl polyethers with which this invention is con-' EPOXIDE RESIN-AMIDE COMPOSITIONS cerned are now. well known and need not. be discussed at William J. Belanger, Louisville, Ky., assignor to Devoed: length herein. The most useful of these epoxide; resins Raynolds Company, inc, a-corporation of New York is made from thereaction of a, polyhydric phenol with» No Drawing. Application November 18, 1957 epihalohydrin or glycerol dihalohydrin and a su?icient ' Serial No. 696,951 amount of a caustic alkali to combine with the halogen 4 Claims. ((1260-47) of the halohydrin. Products resulting from the reaction, This invention relates to heat curable compositions of of a polyhydric phenol with, epichlorhydrinvor glycerol matter particularly suitable for the formation of- castings, dichlorhydrin are monomeric or straight chain‘polymeric, pottings, and thin ?lms as used in coatings, adhesives 10 products. characterized by the presence of more than one, and the, like. More particularly’. the invention is con epoxide group, i.e., a 1,2-epoxy equivalency, greater than cerned with compounding and reacting glycidyl poly one. Dihydric phenols that can be used for this purpose ethers with selected amides to form intermediates having include bisphenol, resorcinol, catechol, hydroquinone, epoxide groups as well as valuable insoluble, infusible methyl resorcinol, 2,2-bis(4-hydroxyphenyl'),butane, 4,4’ cured products. 15 dihydroxybenzophenone, bis(4-hydroxyphenyl)ethane, It is known to use amides as curing agents for glycidyl and 1,5-dihydroxy naphthalene, The preparation of polyethers, particularly amides which are believed to polyepoxides from polyhydric phenols and epihalohydrin decompose. However, reactions involving glycidyl poly is described in US. Patents 2,467,171, 2,538,072, ethers and these amides. are quite sluggish. Representa 2,582,985,, 2,615,007. and. 2,698,315, the proportion. of. tive amides of this type are dicyandiamide, which is a 20 halohydrinI to dihydric phenol being. at least about, 71.2, dimer of cyanamide, and benzoguanamine, derived from to 1, up toaroundlO to 1_. V '1; melamine, which is an amide of cyanuric acid. Mel Higher melting point resinsv are made from the reaction amine is 2,4,6-triamino-1,3,5-triazine, whereas the amide of such resins with a further. amount; of-dihydric- phenol benzoguanamine is 4,6-diamino-2-phenyl-1,3,5-triazine. less than that equivalent to the epoxide content of the When these amides are used with glycidyl polyethers, 25 resin, as set forth in U.S. Patent 2,615,008. Halohydrins even if a solvent is‘employed, the reaction is too slow for can be further exempli?ed by 3-chloro-1,2-epoxy butane, many purposes. In accordance with this invention, how 3-bromo-1,2-epoxy hexane, 3-chloro_-1,2-epoxy octane ever, glycidyl polyethers are reacted with dicyandiamide and the like. Another group of glycidylv polyethers is or benzoguanamine in the presence of special accelera~ produced by the reaction of a polyhydric alcohol with tors. Ithasheen found that quaternary salts 30 epichlorhydrin or glycerol dichlorhydrin as disclosed in are capable of accelerating or activating the reaction Zech patent US. 2,581,464. While the invention, is ap between glycidyl polyethers; and these amides. When plicable to epoxides generally, preferred polyepoxid'es are benzoguanamine. or dicyandiamide is used in combina glycidyl polyethers of aromatic polyhydric compounds tion with these activators, they display surprisingly in having Weights per epoxide group of- 180 to 2000.‘ creased activity as curing agents for glycidyl polyethers. 35 In carrying out the’ process of this invention, the glyci The invention thus provides: a process; for curing, glycidyl dyl polyether and benzoguanamine or dicyandiamide are polyetherswhich- includes mixing and reacting the glycidyl heated; together until a homogeneous composition is polyether, benzoguanamine or dicyandiamide, and, as an formed, generally at a temperature in the range of; 140° activator for the amide, a quaternary ammonium salt. C. to 180°- C., and ‘then the quaternary ammonium salt Quaternary ammonium salts are those salts of strong, 40 is added. No particular difficulties are encountered; ex and weak. organic and inorganic acids. Included are cept those due to the limited-'solubilities of'dicyandiamide such acids asacetic, oxalic, formic, furnaric, benzoic, and and benzoguanamine. Accordingly, when ?lms of inter“ maleic, as well as hydrochloric, phosphoric, sulfuric, and mediate epoxide resins, to be described, are‘preparem'it hydrobromie acids, having pK values not exceeding’ six. will be desirable to use a, solvent». In the case of castings, These quaternary ammonium salts are well known tetra no solvent- is employed; Whena solvent is used,v astrong alkyl, aryl trialkyl and: alkar-yl trialkyl ammonium salts 45 solvent is necessary because of‘ the solubility character of acids having pK valuesnot exceeding six, wherein. the istics of both of the amides, as well as the glycidyl poly aryl, alkaryl and alkyl- substituents each have no more ether. In other words, a polar solvent is used rather than eight carbon atoms. Typical quaternary ammonium than a non-polar solvent, particularly ethers and ketones, salts. are benzyltrimethyl. ammonium acetate, benzyltri esters being less. desirahlebecause of their possible. teas; ethyl , di(phenyltrimethyl)ammo 50 tion with the amide. For this purpose, suitable solvents nium maleate, di(tolyl trimethyl ammonium)fumarate, are ethers such as. “Dioxane” (glycol ethylene ether)’, the benyltrimethyl ammonium ethyl hexoate, di(benzyltri “Cellosolves” such as ethyl “Cellosolve” (2-ethoxyethan~ methyl ammonium)oxalate, di(benzyltrimethy1 ammo ol), butylmcellosolve” (butoxy ethanol), and “Cello nium)tartarate, benzyltrimethyl ammonium lactate, ethyl solve” acetate (Z-ethoxyet-hanol acetate), ~etc.; ketones ene'bisltrimethyl ammonium acetate), .octyl trirnethyl 55 such as acetone, methyl ethyl ketone, methyl isobutyl ', benzyltributyl ammonium acetate, ketone, diisobutyl ‘ketone, etc.; and mixtures of ketone benzyltrimethyl , benzyltrimethyl solvents and ether solvents with aromatic hydrocarbon , trimethyl benzyl ammonium sul solvents, such as xylene, toluene, benzene, etc. ‘ phates, benzyltriethyl ammonium chloride, tributyl benzyl Of course, when a solvent is used, the reaction tem~ ammonium chloride, tripropyl benzyl ammonium chlo perature cannot be above the boiling point of the solvent‘. ride, tolyl trimethyl ammonium chloride, octyl trimethyl In general, the amide and the glycidyl polyether are're , ethylene bis(trimethyl ammonium acted at temperatures of from 100° C. to 150"~ Q,’ a bromide), ethyl pyridine chloride, etc., preferred salts period of from two to sixteen hours being recommended being quaternary ammonium halides. Also intended are for cures. If it is deemed desirable to increase the rate ion exchange resins containing quaternary ammonium of reaction, it will be necessary to use a higher boiling salts of strong acids. The quaternary ammonium salts point solvent so that the reaction can. be carried out at a are utilized in amounts varying from 0.1 percent to 10 higher temperature.‘ 7 j v ~ percent by weight oflthe glycidyl polyether-amide com The following examples are illustrative. of. adesired position, and more preferably in amounts varying from method of preparing the polyepoxides forming an aspect 0.1 percent to 2 percent by weight of the amide-polyether 70 of this invention. It is understood, of course, thatthe composition. > procedures are exemplary only» and that variations will 2,928,81 1 3 occur'to' those skilled in the art. The glycidyl polyethers EXAMPLE 18 employed in the following examples are prepared in the manner described in US. Patents 2,615,007, 2,615,008, B. 8. 0 2. 0 150 28 B- . 8. 0 2.0 4 150 21 2,582,985 and 2,581,464, by the condensation of varying B _ . 9. 0 1. 0 0 150 35 proportions of epichlorhydrin to bisphenol or polyhydric B. _ . 9. 0 1. 0 0. 4 150 13 G- _ 8. 0 2. 0 ' 0 ‘ 150 36 alcohol and subsequent dehydrohalogenation with sodium C. _ B. 0 2. 0 0. 4 150 20 hydroxide. The table which follows indicates the‘ ratio C- . 9. 0 l. 0 0 150 57 O. _ 0. 0 1. 0 0. 4 150 24 of epichlorhydrin to bisphenol or alcohol used to prepare E - 8. 0 2. 0 0 150 14 the glycidyl polyethers. In the examples and tables which E _ 8. 0 2. 0 0. 4 150 I 9 E _ 9. 0 . 1. 0 U 150 40 follow, BTMACl will be used instead of benzyltrimethyl E _ 9. 0 1. 0 0. 4 150 20 ammonium chloride and the polyepoxides will be referred F. __ 8. 0 2. 0 0 150 21 F. .._ 8.0 2. 0 0. 4 150 3 8 to as Epoxide A, B, C, etc. Thus, Epoxidc A is made F- __ 9. 0 1. 0 0 100 184 from 1.0 mol of bisphenol and 10.0 mols of epichlor F ...... -- 9. 0 1. 0 0. 4 150 20 hydrin, and has an epoxide equivalent‘of 190. 15 1 BTMACl represents benzyltrimethyl ammonium chloride (60 per TABLE OF EPOXIDES cent aqueous solution). 9 Became exceedingly exothermic. , M01 ratio Example 2 . Epoxide Epoxlde Hydroxyl compound , Equiv Epichlor- Hydroxyl alent In a beaker, 9.0 grams of Epoxide B and 1.0 gram of hydrin Com 20 dicyandiamide are heated with stirring at 170° C. until pound a homogeneous melt is obtained. Into the melt is blended 0.4 gram of a sixty percent aqueous solution of benzyl 10.0 1; 0 190 trimethyl ammonium chloride after which the mixture is B 2. 04 1.0 340 ..do-__ 1. 21 1. 0 960 poured into an aluminum cup and is heated in a 150° C. D Trimethylol propane- 2. 0 1. 0 172 oven. Gelation occurs after heating for ten minutes. E _ Glycerol ...... -_ 3. 0 1.0 155 F ...... _- Resorcluol ______10.0 1.0 126 Following the same procedure, from a blend of 9.0 grams of Epoxide B and 1.0 gram of dicyandiamide, without the presence of an accelerator, a gel is obtained Example 1 after heating for twenty minutes at 150° .C. To illustrate e?ectively the use of quaternary ammo Example 3 nium salts as accelerators for the benzoguanamine-glycid yl polyether reaction, gel times are given rather than In accordance with the procedure of Example 1, vary curing times, the gel being the ?rst stage of an infusible, ing amounts of Epoxide A and benzoguanamine are insoluble material. heated until gels result. As accelerators, tetramethyl In a suitable container, the glycidyl polyether and 35 ammonium chloride and benzyltrimethyl ammonium ace benzoguanamine are heated with stirring at a tempera~ tate are employed. For comparison, without the use of tureof about 140° C. until a homogeneous melt is ob an accelerator, compositions are also heated until gels tained, whereupon a catalytic amount of a sixty percent are obtained. ' ' aqueous solution of benzyltrimethyl ammonium chloride The table following indicates the compositions em is blended into the melt. The mixture is poured into an ployed and the length of time the mixtures are heated at aluminum cup and is heated in a 150° C. oven until gela 150° C. to obtain gels. tion occurs. . 2 Following the same procedure but without the addition Benzogua- Quaternary Epoxlde A, namine, Quaternary ammonium Gel Time, .of the accelerator, mixtures of benzoguanamine and weight (grams) weight ammonium salt minutes (grams) salt; - weight epoxides are reacted at elevated temperatures shown and (grams) for such time as to obtain gels. . The tables which follow indicate the composition of 8.0 2. 0 0 56 the mixtures used and the time and temperature required 8.0 2. 0 TMACl I"... 0.4 24 for gelation to occur. 8.0 2. 0 BTMAAc l-.. 0. 4 7 9.0 1. 0 ' 0 190 TABLE 9.0.. _. 1. 0 ‘TMACI in... 0. 4 39 9.0 ...... __ 1.0 BTMAAe i.-- ' 0.4 5 EXAMPLE 1A 1 TMACI represents tetramethyl ammonium chloride (60 percent Benze aqueous solution). Epoxide, gunua- BTMAOI,‘ Temper- Gel 1 BTMAAc represents benzyltrimethyl ammonium acetate (41 percent Epoxide weight mine, weight ature, time 55 aqueous solution). (grams) weight ‘ (grams) ° 0 (mm.) (grams) Among the advantages of this invention is the fact that various epoxide resins can be prepared. If two to four A'..-- 8. 0 2.0 0 150 >150 mols of a glycidyl polyether are used per mol of the A- _ 8. 0 2. 0 0.12 150 64 A" 8.0 2. 0 0. 23 150 33 60 amide, valuable intermediate resinous compositions hav A__ 8.0 2. 0 0 180 30 ing epoxide groups are obtainable. These intermediates A“ 8.0 2.0 0. 12 180 15 A“ 8.0 2.0 0. 23 180 7 polyepoxides are distinguishable from the cured compo A" 8. 5 1. 5 0 125 525 sitions because of the existence of epoxide groups which A" 8. 5 1. 5 0. 12 125 240 A" 8. 5 1. 5 0. 23 125 125 can be identi?ed. In addition, they are not insoluble and A- _ 8. 5 1. 5 0 150 525 A..- 8.5 1. 5 0. 12 150 115 65 infusible, but, rather, undergo reactions characteristic A" 8. 5 1. 5 0. 23 150 75 of other epoxide resins. Thus, the intermediate compo A. . 8. 5 1. 5 0 180 85 A. - 8. 5 1. 6 0.12 180 55 sitions can be further modi?ed, heat cured to an insoluble, A-- 8. 5 1. 6 0.23 180 15 infusible state, or more rapidly cured with known epoxide A-.. 9. 0 1. 0 0 125 525 A..- 9. 0 1. 0 0. 12 125 180 curing agents such as amines as seen in Example 10. A" 9. 0 1. 0 0. 23 125 120 70 In accordance with this embodiment of the invention, A" 0. 0 1. 0 0 150 525 A" 9. 0 1. 0 0Q 12 150 116 intermediate epoxides having a variety of epoxy equiva A... 9. 0 1. 0 0. 23 150 60 leuts are possible. The glycidyl polyether, the amide and A...- 9. 0 1. 0 0 180 180 A"-.. 9.0 1.0 0.12 180 55 the quaternary ammonium salt, with or without a sol ‘A ...... _. 9. 0 ' 1. 0 0. 23 180 15 vent, are reacted at elevated temperatures for such pe 75 riods as ‘to obtain intermediate epoxide resins of desired aeaaa 1 i 5 6 or theoretical epoxy equivalencies, the epoxy equivalent Example 77 I being governed by periodic determinations being made during the course of the reaction. The composition when Weight ' Molar cooled is the desired intermediate epoxide resin, interme - ratio diate resins having epoxy equivaiencies in the range of 230 to 1000 being obtainable. The preparation of these Epoxide A ...... - - 4 Benzoguanamine 1

intermediates can best be illustrated by reference to the Dioxane ...... - - following examples. 2-ethoxyethan ' _ A0 ...... -- 5.0 grams of a 60 percent aqueous solution. - Example 4 10 Following the procedure of Example 4, an intermediate Weight- Molar epoxide resin is prepared by heating at 1209 C.‘ for ?fteen ratio hours the Epoxide A and the benzoguanamine in the presence of Dioxane and benzyltrimethyl ammonium Epoxide A._ 380.0 grams _ 7 - - ‘ 2 Benz0guanamine__-. 93.5 grams ______> ______-- 1 15 chloride. Before ?ltering, the Z-ethoxyethanol'is added. “ Dioxane”_ 474.0 grams I . The intermediate resin solution has a viscosity of Z; BTMACll ______._ 2.5 grams of a 60 percent aqueous solution...... {Gardner-Holdt) at' a non-volatile content of sixty per cent as determined by heating for one .hour at 180° C. Into a one liter, three-necked, round bottomed'?ask The epoxide resin, based on solids, has an equivalent ?tted with a mechanical agitator, thermometer and re?ux weight per epoxide group of 476. condenser are charged the Epoxide A, benzoguanamine, a portion (125.0 grams) of the Dioxane and the benzyl Example 8 trimethyl ammonium chloride solution. The ?ask con tents are heated to re?ex temperature (about 128° C.) Weight Molar and are maintained at re?ux for seven hours after-which ratio the clear viscous reaction mixture is cooled to room tem 25 Epoxide F___ - 101.0 grams’ 4 perature, the remainder (349.0 grams) of the Dioxane Benzoguanamine__._ ‘18.7 grams...- _____ -. ______.- ...... >.. 1 is added and the solution is ?ltered. The?ltered inter~ Dimmnp 60,0 grn'ms ‘ > ’ mediate epoxide resin solution has a viscosity ofU-V BTMACI ...... __ 1.4 grams of a 60 percent aqueous solution...... (Gardner-Holdt) and a solids content of 57 percent as determined by heating for one hour at 1809 C. The 30 Following the procedure of Example’4, an intermedi intermediate epoxide resin prepared has an epoxide ate epoxide resin is prepared by re?uxing for four hours equivalent of 499 (based on solids). at 130° C. the Epoxide F, benzoguanamine, Diox'ane and benzyltrimethyl ammonium chloride solution. ‘ The Example 5 ?ltered intermediate epoxide resin solutio'n'has' a' viscosity 35 of U (Gardner-Holdt) at 75.8 percent solids contentva‘s Weight Molar determined by heating at 180° C. for one hour. ' The ratio epoxide resin has a weight per epoxide group of 248 Epoxide A. 380.0 grams 3 (based on solids). Benzoguanamine._-. 62.5 grams ...... -. 1 - Example 9 Dionne 443.0 grams 40 BTMACI ...... _ 2.5 grams of a 60 percent aqueous solution...... From the intermediate epoxide resin solutions of the preceding examples, ?lms are drawn'down on a glass Following the procedure of Example 4, an intermedi plate with a three mil blade and are cured by baking ate epoxide resin is prepared by re?uxing for six and a at 180° C. for twenty minutes. half hours the Epoxide A and benzoguanamine in the The table which follows lists the physical properties presence of a portion (125.0 grams) of the Dioxane and of the corresponding cured ?lms. the benzyltrimethyl ammonium chloride solution. Before ?ltering, the remainder (318.0 grams) of Dioxane is Epoxide resin Hardness Flexibility Adhesion Mar added. The ?ltered solution has a viscosity of B (Gard~ of- resistance ner-Holdt) and a solids content of 53 percent as deter - Example4 ______Excellent“ Good ______Very good__ Very good. mined by heating for one hour at 180° C. The epoxide Example 5 ...... do ...... _.do ______.-do ____ .. Do. equivalent of the intermediate epoxide resin prepared Example 6 ______Good ______Very good..- .-__-do ____ _. Do. (based on solids) is 394. ‘ Example 6 Example 10 To portions of the previously prepared epoxide resin Weight Molar solutions are added one equivalent weight of tetraethyl ratio ~ enepentamine and from the resulting‘ blends, ?lms are drawn down on a glass plate and are cured’ by heating Epoxide D 137.6 grams 4 for twenty minutes at1180° C. Benzoguanamine__.. 18.7 grams ______1 imrmw 106.3 Frame 60 The table following enumerates the physical properties Toluene 50.0 grams B'I‘MACl ______1.0 gram of a 60 percent aqueous solution- ______of the corresponding cured ?lms prepared.

Epoxide resin Hardness Flexibility Adhesion Mar An intermediate epoxide resin is prepared as described of- resistance in the procedure of Example 4 by re?uxing for eight 65 hours the Epoxide D and benzoguanamine in the pres Example 4 ______Exeellent__ Good ..... -. Very good__ Very good. Example 5 ...... "do ____ -. Very good.. __...do .... _. Do. ence of a portion (50.0 grams) of the'Dioxane and the Example 6 _____ ._ Good ______._do ...... do ____ ._ Good. benzyltrimethyl ammonium chloride solution. Before ?ltering, the remainder (56.3 grams) of the Dioxane and I The foregoing examples show that epoxide resins hav~ the toluene are added. The intermediate epoxide resin ing a wide range of epoxide equivalents can ‘be prepared solution has a viscosity of E (Gardner-Holdt), the solids in accordance with this invention. In addition, the ratio content being 53.7 percent as determined ‘by heating for of glycidyl polyether to amide varies widely depending one hour at 180° C. The intermediate epoxide resin upon whether intermediates or cured compositions are prepared has a weight per epoxide group of,533 (based prepared. As indicated hereinbefore, from two to four on solids). 75 mols of glycidyl polyether are employed per mol of agree;

. 7 . , ,, 8 amide when intermediate epoxides are made. However, considering an epoXide equivalent glycidyl polyether as cured compositions are obtained using more than four the weight in grams of polyether per epoxide group. mols of glycidyl polyether per mole of amide. Up to 2. The processof claim 1_wherein the glycidyl poly ten mols can be used, although not with equivalent re ether has an epoxide equivalent, not exceeding one thou sults. In other words, from 0.1 to 0.5 mol of amide can sand and wherein‘ the activator is an aryl trialkyl am be used per mol of glycidyl polyether. monium halide‘, s Intermediate epoxides of this invention can be reacted 3. The process of claim 2 wherein the glycidyl poly with compounds having any of the functional groups such ether has an epoxide equivalent of 180 to 250 and as carboxyl, amine, and phenolic substituents, for exam wherein the aryl trialkyl ammonium halide is benzyl tri ple, diethylene triamine, oxalic acid, BPS monoethyl 10 methyl ammonium chloride. amine, etc. In addition, the epoxides can also be heat 4. A heat curable composition of matter comprising cured to form ?lms having properties making them use a glycidyl polyether of a polyhydric compound of the ful in ‘the coatings ?eld. Obviously, many modi?cations group consisting of polyhydric phenols and polyhydric and variations of the invention as hereinbefore set forth alcohols, said polyether having-an epoxide equivalency can be made without departing from the spirit and scope 15 greater than'oneand,anjepoxide, equivalent not exceed thereof, and, therefore, such modi?cations are deemed ing two thousand, an amide selected from the group con to be within the scope of this invention. sisting of benzoguanamine and vdicyandiarmide, and from ~ ‘What is claimed is: 0.1 to 10 percent based" on the polyethef-amide mixture 1. In the process for resinifying and curing a glycidyl of a ‘quaternary-ammonium salt selected from the group polyether of a polyhydric compound of the group con 20 consisting- of tetra'alkyl, aryl trialkyl, and alkaryl tri sisting of polyhydric phenols and polyhydric alcohols, alkyl ammonium salts of acids having pK values not ex said glycidyl polyether having an epoxy equivalency ceeding six, wherein the aryl alkaryl and alkyl sub~ greater than one and an epoxide equivalent not exceed stituents have no more than eight carbon atoms, con ing two thousand, wherein the glycidyl polyether is sidering an epoxide equivalent as the weight in grams of mixed and heat reacted with an amide selected from the 25 polyether per epoxide group. group consisting of benzoguanamineand dicyandiamide, the improvement 'which' comprises cheat, reacting the ~ I References ‘Cited in the ?le of this patent glycidyl polyether and the amide utilizing as an ac ,UNITED STATES PATENTS celerator for the reaction 0.1 to 10 percent, by weight 2,155,269- Condo et al. ______June 26, 1956 based on the poiyether-amide mixture, of an activator 2,768,992 v Zukas ______Oct. 30, 1956 consisting of a quaternary ammonium salt selected from 2,865,886 Greenlee ______.._ Dec. 23, 1958 the group consisting of tetra-alkyl, aryl trialkyl and alk aryl trialkyl ammonium salts of acids having pK values FOREIGN PATENTS not exceeding six, wherein the aryl, alkaryl and alkyl 133,819 Australia ______.... July 15, 1945 snbstituents have no more than eight carbon atoms, 35