NZ244069A

NZ244069A - Flexibilized epoxy resin comprising a residue of at least one polyaromatic hydroxy compound and at least one polyglycidyl ether of such compounds and a polybutylene glycol derivative; electrodeposition coatings

Info

Publication number: NZ244069A
Application number: NZ244069A
Authority: NZ
Inventors: Henry G Heck; Aarnout Cornelis Rouw
Original assignee: Dow Chemical Co
Priority date: 1991-08-26
Filing date: 1992-08-24
Publication date: 1995-04-27
Also published as: AU2507292A; CA2114795A1; ZA926412B; EP0601069A1; MX9204931A; BR9206473A; WO1993004104A1; KR940702200A; JPH06510079A

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £44069 % f4 . - ' • ' . A • A -. M'. • - .V--. . 27 APR 1995 P.O. *** f'« \ VM NO DRAWINGS' 2 • iw ■ HECCIV".! NEW ZEALAND PATENTS ACT, 1953 No.: Date: COMPLETE SPECIFICATION INTERNALLY FLEXIBILIXED ADVANCED EPOXY RESIN COMPOSITIONS AND COATINGS THEREFROM We, THE DOW CHEMICAL COMPANY of 2030 Dow Center, Abbott Road, Midland, Michigan 48640, United States of America, a corporation organized and existing under the laws of the State of Delaware, United States of America, hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- - 1 - (followed by page la) /. h A ft i f * « ' . "7 SJ U ki INTERNALLY FLEXIBILIZED ADVANCED EPOXY RESIN COMPOSITIONS AND COATINGS THEREFROM The invention relates to internally flexibilized advanced epoxy resin compositions flexibilized with internal polybutylene glycol units* and a process for the preparation of such internally flexibilized advanced epoxy resins. The invention further relates to coatings prepared from such internally flexibilized advanced epoxy resins, such coatings are useful in cathodic electrodepositions, powder coating applications, marine and maintenance and in food and beverage applications. variety of applications, such as in coatings compositions in several fields, for example in cathodic electrodeposition, powder coating of pipes and 20 structural elements, in liquid coating compositions for food and beverage cans and marine and maintenance applications. Advanced epoxy resin based coatings have advantageous properties such as adhesiveness, strength, hardness and chemical resistance. Unfortunately, cured 15 Advanced epoxy resin compositions are used in a 25 C-39,A62-F 2 advanced epoxy resin compositions suffer from a lack of flexibility, which can have a negative effect on other properties such as protection of substrates from corrosion. 5 A representative use of advanced epoxy resins compositions which exhibits such problems is the field of cathodic electrodeposition. Cathodic eLectrodeposition of a film composed of an amine modified epoxy resin, crosslinker, pigment and optionally other resinous components onto an electrically conductive article is an important industrial process. It constitutes the usual manner in which automobile and truck bodies as well as appliance and other large complex metallic surface bodies are protected against corrosion. In performing the electrodeposition, the conductive article, article to be coated, forms one electrode and is immersed in a coating 20 bath made from an aqueous dispersion of the film forming amine modified epoxy resin and other components. An electrical current is passed between the article and the counterelectrode in the electrodeposition bath. A charge on the article causes deposition of the resins and other ?5 components in the bath on the article to be coated so as to produce the electrodeposited film. The deposited film is then baked or otherwise hardened to yield a coating of a substantially uniform thickness and protective characteristics. A number of advances in the protective properties of electrodeposit resin systems have been described in the patent literature. For example, US Patent Nos. 4,104,147; 4,148,772; 4,420,574; 4,423,166; C-39,462-F 2 4 3,962,165; 4,071,428; 4,101,468; 4,134,816; 3,799,854; 3,824,111; 3,922,253; 3,925,180; 3,947,338; 3,947,339, describe methods for improvement of the principal resin properties. Amine modified epoxy resins used in the coatings disclosed in these patents can be flexibilized 3 by extending the molecular length of the aromatic diepoxide starting material with polyols, polyamines, polyether polyols, polyester polyols and other similar types of extension agents. US Patent 3,839,252 describes modification with polypropylene glycol. US Patent 3,947,339 teaches modification with polyesterdiols or polytetramethylene glycols. US Patent 4,419,467 describes still another modification with diols derived from cyclic polyols reacted with ethylene oxide. In 15 those embodiments wherein polyether polyols and polyester polyols have been used to modify the advanced epoxy resins, it has been difficult to efficiently and effectively incorporate such materials into the backbone of the resin. Tertiary amines or strong bases are 20 required to effect the reaction between the primary alcohols and the epoxy groups involved. Furthermore, these reactions require long cook times and are subject to gellation because of competitive polymerization of the epoxy groups by the base catalyst. In addition epoxy resins containing low levels of chlorine are required to prevent deactivation of this catalyst. European Patent Application 300,504A discloses 2q the preparation of flexibilized epoxide compounds by reacting an aromatic diol with diepoxides which are diglycidyl ethers of aromatichydroxy compounds, or a bis-(labile hydrogen functionalized) alkoxy arylene compound. European Patent Application 315,164 discloses a coating resin composition which comprises the reaction C-39,462-F 3 4 10 product of a diepoxide compound which is a diglycidylether of a bisphenol A (bis-(4-hydroxy phenyl)propane) initiated polyalkylene oxide, a bisphenol, optionally a bisphenol diglycidylether, and an amine, having an active hydrogen. It is disclosed therein that the bisphenol A initiated polyalkylene oxide diepoxide results in an improved electrodeposition coating. Commonly assigned patent application EP 253,405 discloses an advanced epoxy cationic resin prepared by reacting in the presence of a suitable catalyst (A) a composition comprising (1) at least one diglycidyl ether of a polyol and (2) at least one diglycidyl ether of a dihydric phenol with (B) at least one dihydric phenol and optionally (C) a monofunctional capping agent. 15 Components (A) and (B) are employed in such quantities that the resultant epoxy resin has an average epoxide weight from 350 to 10.000. 20 The resins disclosed exhibit some flexibility problems and do not provide superior anticorrosion properties. Additionally, some of the processes disclosed for preparing the resins do not efficiently 25 incorporate the polyalkylene glycol containing diepoxides into the backbone of the advanced resins. 30 In electrodeposition it is desirable that the resins in the coating have a low viscosity to facilitate processing and control of the coating thickness. It is also desirable that such coatings demonstrate low water permeability as this property is important in the inhibition o£ corrosion. Additionally it is desirable C-39,462-F 4 D that such coatings demonstrate good flexibility. The problem is that as the resin viscosity is lowered and the coating flexibility is increased, the water permeability of the coating is usually also increased. What is needed are resins for use in coatings, including 3 electrodeposition coatings, which exhibit lower viscosities, result in coatings with higher flexibility and lower water permeability. What is further needed, is an advanced resin which has efficiently incorporated therein the flexibilizing agents. What is further needed is a process which allows efficient incorporation of the flexibilizing agent into the backbone of the advanced epoxy resin. 15 The invention relates to flexibilized advanced epoxy resins comprising the residue of A. one or more polyglycidyl ethers of a water 20 or di- or trihydroxy substituted Ci-e hydrocarbon initiated polybutylene glycol; B. one or more polyaromatichydroxy compounds; and 25 C. one or more polyglycidyl ethers of polyaromatichydroxy compounds; wherein substantially all of the glycidyl ether moieties 30 of the polyglycidyl ethers of polybutylene glycol are bound to the polyaromatichydroxy compounds through the reaction product of the glycidyl ether moieties with the aromatichydroxy moieties; C-39,462-F 5 2 44 o 25 30 each poLyaromatichydroxy compound is bound to at Least one poLygLycidyl ether of poiybutyLene glycoL or to at least one polyglycidyl ether of a polyaromatichydroxy compound through the reaction product of an aromatichydroxy moiety with a glycidyl ether moiety; each residue of a polyglycidyL ether of poLyaromatichydroxy compound is bound to at Least one polyaromatichydroxy compound through the reaction of a glycidyL ether moiety and an aromatichydroxy moiety; wherein the moLe ratio of poLyaromatichydroxy compound to poLygLycidyl ether of poiybutyLene gLycoL is 2.0 or 'nore to 1.0; and sufficient poLygLycidyl ether of polyaromatichydroxy compound is present in the resin such that the terminal moieties of the resin are 20 glycidyl ether moieties from the poLygLycidyl ethers of polyaromatichydroxy compounds. In another aspect the invention is a process for the preparation of such fLexibiiized advanced epoxy resins comprising A. reacting a poLygLycidyL ether of a di- or tri- hydroxy C^_6 hydrocarbon or water initiated poLybutyLene glycoL with two or more moLes of a poLyaromatichydroxy compound per moLe of poLygLycidyL ether of poLybutyLene gLycoL under conditions such that substantialLy alL of the gLycidyl ether moieties of the poLygLycidyL ether of poLybutyLene gLycoL react with C-39,462-F 6 > ) -I 7 aromatichydroxy moieties of the polyaromatichydroxy compounds; B. thereafter reacting the reaction product from A with an excess of one or more polyglycidyl ethers 5 of polyaromatichydroxy compounds, optionally one or more polyaromatichydroxy compounds, and optionally one or more chain terminators, under conditions such that the aromatichydroxy moieties react with the glycidyl ether moieties wherein the terminal functional moieties of the ^ product are glycidyl ether moieties. In another aspect the invention relates to 15 flexibilized advanced epoxy resins prepared by the above-described process. In yet another aspect the invention is directed to advanced epoxy cationic resins having a charge density of from 0.2 to 0.6 milliequivalents of cationic charge per gram of resin, 20 wherein the terminal epoxy moieties of the above-described resins have been reacted with a nucleophile and treated to render the resulting moieties cationic. 25 The advanced epoxy resins of the invention demonstrate improved flexibility and improved corrosion protection of substrates coated with such compositions as compared to conventional resins. The flexibilized ^ advanced epoxy resin compositions of the invention and the process for preparation of the resin also demonstrate a more efficient incorporation of the flexibilizing agent into the backbone of the resin. The flexibilized advanced epoxy resins of the invention demonstrate improved elongation and impact resistance C-39,462-F 7 8 10 along with exceptional combination of elongation, impact resistance, and corrosion resistance as compared to conventional resins. A major advantage of the invention is the efficient incorporation of an improved flexibilizing agent into the internal backbone of the advanced epoxy resins. Thus the backbone of the flexibilized epoxy resin of this invention contains at least one unit of the flexibilizing component in its interior. The flexibilizing unit is the residue of a polyglycidyl ether of a water or di- or tri- hydroxy substituted Cj.-6 hydrocarbon initiated polybutylene glydol, which means herein that the glycidyl ether moieties of such compound have been reacted with aroraatichydroxyl groups so as to incorporate such polybutylene glycol into the backbone of the flexibilized advanced epoxy resins. The flexibilizing agent is prepared by reacting water or a di- or tri- hydroxy substituted Ci-6 hydrocarbon with 20 butylene oxide units, so as to react the hydroxy units or water with the butylene oxide, thereby forming a polybutylene glycol with a central unit comprising oxygen or the residue of the di- or tri- hydroxy substituted Ci-6 hydrocarbon. Thereafter the terminal hydroxy moieties of the polybutylene glycol are reacted with an epihalohydrin to form terminal glycidyl ether moieties. Such reactions are well-known to those skilled in the art. Polybutylene glycol as used herein refers to compounds which contain more than one butylene oxide unit within the backbone, and includes compounds wherein one butylene oxide unit is added to each active hydrogen unit of the initiator. 25 30 C-39,462-F 8 9 Included among the initiators for the flexibi1izing unit are water, ethylene glycol, propylene glycol, butane diols, such as 1,4 butane diol, trimethyol propane, neopentylglycol and glycerol. The most preferred initiator is water. Preferably, the 3 polyglycidyl ether of polybutylene glycol has a molecular weight of 140 or greater, most preferably 200 or greater and most preferably 300 or greater. Preferably the polyglycidyl ether of polybutylene iq glcyol, has a molecular weight of 2000 or less, more preferably 1000 or less, and most preferably 600 or less. The molecular weights referred to here are number average molecular weights. The flexibilized advanced epoxy resins of this invention preferably contain 5 15 percent or greater by weight of the residue of the glycidyl ethers of polybutylene glycol in the backbone, and more preferably 10 percent or greater. Preferably, the flexibilized advanced epoxy resins of this invention contain 50 percent or less by weight of the residue of 20 polyglycidyl ethers of polybutylene glycol in the backbone, more preferably 30 percent or less by weight. In a preferred embodiment, the glycidyl ethers of polybutylene glycol correspond to formula 1: wherein R is independently in each occurrence hydrogen, methyl or ethyl with the proviso that for each 25 1 R R C-39,462-F 9 10 unit either both of R are methyl or one R is ethyl and the other is hydrogen; T is independently in each occurrence a direct bond or the moiety 5 R' —COCH2— i:H2ci 10 R1 is independently in each occurrence hydrogen or a alkyl moiety; Z is independently in each occurrence oxygen or X is independently in each occurrence a straight or 20 branched chain C1-6 alkyl moie ty; a is independently in each occurrence a positive real number of 1 or greater; b is independently in each occurrence 2 or 3. Z is preferably oxygen. X is preferably a straight or branched chain C1-4 alkyl moiety. Preferably, a is a real number of from 1 to 16; more preferably from 1 to 2q 8 and most preferably of from 2 to 5. Preferably b is 2. The initiator used in this invention preferably is water or corresponds to Formula 2: C-39,462-F 10 11 3 vherein X and b are as described hereinbefore. The polyglycidyl ethers of polybutylene glycol are reacted with polyaromatichydroxy compounds. 10 Polyaromatichydroxy compounds referred herein to compounds which on average contain more than one hydroxy group and which comprises a hydrocarbon backbone containing aromatic moieties, wherein the hydroxy moieties are bound to aromatic moieties directly. ^ Preferably the polyaromatichydroxy hydrocarbons have two or more aromatic bound hydroxy groups. The polyaromatichydroxy compounds can be further substituted on the hydrocarbon backbone by halogen moieties. Among 2q preferred classes of polyaromatichydroxy compounds are the bisphenols, halogenated bisphenols, hydrogenated bisphenols, and novolac resins, i.e. the reaction product of phenols and simple aldehydes, preferably formaldehyde and hydroxy benzaldehyde. Preferred 25 polyaromatichydroxy compounds useful in this invention correspond to formula 3: Ar—(OH)c 3 30 wherein Ar is an aryl moiety; aryl moiety substituted with an alkyl or halo moiety; a polyaryl moiety wherein the aryl moieties are connected by direct bonds, alkylene, C-39,462-F 11 10 12 haloalkylene, cycloalkylene, carbonyl, sulfonyl, sulfinyl, oxygen, or sulfur moieties, such polyaryl moieties being optionally substituted with an alkyl or halo moiety; or the oligomeric reaction product of an aldehyde and phenol; and c is a positive real number greater than 1. More preferred polyaromatichydroxy compounds incLude those corresponding to formulas 4 and 5: 15 \ i C-39,462-F 12 ... n 10 25 30 13 wherein; R2 is separately in each occurrence Ci_3 alkyl or a halogen; R3 is separately in each occurrence Ci-io alkylene, Ci-1,0 haloalkylene, C4-10 cycloalkylene, carbonyl, sulfonyl. sulfinyl, oxygen, sulfur, a direct bond or a moiety corresponding to the formula 15 R4 is independently in each occurrence Ci-io alkylene or C5-50 cycloalkylene; 20 q is independently in each occurrence a C1—10 hydrocarbyl moiety; Q' is independently in each occurrence hydrogen, cyano, or a C1-16 alkyl group; m is independently in each occurrence an integer of 0 to A; m' is independently in each occurrence an integer of from 0 to 3; p is a positive real number of 0 to 10. R3 is preferably C1-3 alkylene, C1-3 haloalkylene, carbonyl, sulfur, or a direct bond. R3 is more preferably a direct bond, C1-3 alkylene, or fluorinated propylene (=C(CF3)2-). R3 is most preferably propylene. R2 is preferably methyl, bromo or chloro; and C-39,462-F 13 14 most preferably methyl or bromo. R4 is preferably C1-3 alkylene or polycyclic moiety corresponding to the formula 30 10 wherein t is an average number from 1 to 6 inclusive, preferably 1 to 3, most preferably 1. Preferably, m and m1 are independently an integer of 0 to 2. Preferably, p 15 is a positive real number of 0 to 8; and more preferably 0 to 4. p represents an average number, as the compounds to which it refers are generally found as a mixture of compounds with a distribution of the units to which p refers. Cycloalkylene as used herein refers to o n monocyclic and polycyclic hydrocarbon moieties. The most preferred class of polyaromatichdroxy compounds are the dihydroxy phenols. Preferable dihydroxy phenols include those which contain substituents that are non-reactive with the phenolic groups. Illustrative of such phenols are 2,2—bis(3,5— dibromo-4-hydroxyphenyl) propane; 2,2-bis(3,5-dibromo-2,4'-hydroxyphenyl) propane; 2,2-bis(4-hydroxyphenyl) propane; 2,2-bis(2,4'-hydroxyphenyl) propane; 2,2-bis(3,5-dichloro-4-hydroxyphenyl) propane; 2,2—bisC3,5— dichloro-2,4'-hydroxyphenyl) propane; bis (4-hydroxyphenyl) methane; bis (2,4'-hydroxyphenyl) methane; 1,l-bis(4-hydroxyphenyl)-l-phenyl ethane; 1,1-bis(2,41-hydroxyphenyl)-l-phenyl ethane; l,l-bis(2,6- C-39,462-F 14 15 dibromo-3,5-dimethyl-4 hydroxy phenyl) propane; bis (4-hydroxyphenyl) sulfone; bis (2,41-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) sulfide; bis (2,4'-hydroxyphenyl) sulfide; resorcinol; hydroquinone; and the like. The preferred dihydroxy phenolic compounds are 3 2,2-bis(4-hydroxyphenyl) propane, 2,2-bis(2,4'- hydroxyphenyl) propane (a mixture of the two is commonly referred to as bisphenol A). 10 As used herein haloalkyl refers to a compound with a carbon chain and one or more of the hydrogens replaced with a halogen, and includes compounds where all of the hydrogen atoms have been replaced by halogen atoms. Alkylene as used herein refers to a divalent alkyl moiety. The term hydrocarbyl means any aliphatic, 2q cycloaliphatic, aromatic, aryl substituted aliphatic or cycloaliphatic, or aliphatic or cycloaliphatic substituted aromatic groups. The aliphatic groups can be saturated or unsaturated. Likewise, the term hydrocarbyloxy means a hydrocarbyl group having an 25 oxygen linkage between it and the carbon atom to which it is attached. Polyaryl moiety as described herein refers to compounds which contain more than one aromatic ring which may be fused, bonded by direct bond, or connected by alkylene, haloalkylene, cycloalkylene, ^ carboxyl, sufonyl, sulfinyl, oxygen or sulfur moieties. The term residue as used herein refers to the portion of a starting material remaining in the final product after completion of the reaction. The term C-39,462-F 15 •l * & 16 10 13 30 residue of a polyaromatichydroxy compound means herein that a polyaromatichydroxy compound has been incorporated into the backbone of the flexibilized advanced epoxy resin wherein the aromatichydroxy moieties have reacted with glycidyl ether moieties of the glycidyl ether of polybutylene glycol, or the glycidyl ether moieties of a glycidyl ether of an aromatichydroxy compound. In a preferred embodiment, the polyaromatichydroxy compounds are nominally dihydroxy aromatic compounds meaning that the dihydroxy compounds are a mixture of compounds resulting from the preparation process, and on average the compounds present have near two hydroxy moieties per molecule. The residue of polyglycidyl ethers of polyaromatic hydrocarbon means herein that at least one of the glycidyl ether moieties has reacted with an aromatichydroxy moiety, wherein the polyaromatichydroxy 20 compound may be further reacted with a polyglycidyl ether of a polybutylene glycol. The resins of this invention preferably have terminal glycidyl ether moieties which are derived from the glycidyl ethers of polyaromatichydroxy compounds. A small portion of the flexibilized advanced epoxy resins of this invention contain polyglyciyl ethers of polyaromatic hydrocarbons that have not reacted with an aromatichydroxy moiety. Generally these materials are not removed prior to utilization. Polyglycidyl ether of a polyaromatichydroxy compound means a hydrocarbon compound containing one or more aromatic moieties, wherein more than one epoxy (1,2 glycidyl ether) moiety is bound to the aromatic C-39,462-F 16 17 moieties. In another embodiment it refers to a mixture of compounds which contains, on average, more than one epoxy moiety per molecule bound to aromatic moieties. Polyglycidyl ether of a polyaromatichydroxy compound as used herein includes partially advanced epoxy resins 3 i.e. the reaction of a polyglycidyl ether of a polyaromatichydroxy compound and one or more polyaromatichydroxy compounds, wherein the reaction product has an average of more than one unreacted epoxide unit per molecule. Polyglycidyl ethers of a polyaromatichydroxy compounds (polyepoxides) are prepared by reacting an epihalohydrin with a polyaromatichydroxy compound. The preparation of such compounds is well known in the art. See Kirk-Othmer Encyclopaedia of Chemical Technology 3rd Ed. Vol. 9 pp 267-289, "The Handbook of Epoxy Resins" by H. Lee and K. Neville (1967) McGraw Hill, New York, and 20 US Patents 2,633,458; 3,477,990; 3,821,243; 3,907,719, 3,975,397; and 4,071,477. The epihalohydrins correspond to formula 6: 25 30 C-39,462-F 17 R1 I ch2 — cch2y wherein 10 Y is a halogen, preferably chloro or bromo, and most preferably chloro; and R' is as previously defined. The polyglycidyl ethers of polyaromatichydroxy 15 compounds useful in the invention preferably correspond to formula 7 R1 20 aho-CH2^-ch2)c o wherein Ar, R1 and c are previously defined. R1 is 25 preferably hydrogen or methyl. Preferably, c is 5 or less, more preferably from 1 to 3. The polylycidyl ethers of polyaromatichydroxy 30 compounds more preferably correspond to one of formulas 8 or 9: C-39,462-F 18 19 8 s' CHiCCH->0 wherein Rl, R2, R3, RS m, and m1 are as defined 25 previously; r is a positive real number of 0 to 40; and s is a positive real number of 0 to 10. Preferably, r is a positive real number of 0 to 10, and most preferably 1 to 5. Preferably, s is a positive real number of 0 to 8; 30 and most preferably 1 to 4. All of the variables referred to herein as positive real numbers, i.e. r and s, are average numbers as the compounds referred to contain a distribution of units. Preferable polyglycidyl ethers of polyaromatichydroxy compounds are the glycidyl ethers of C-39,462-F 19 20 10 dihydroxy phenols, bisphenols, halogenated bisphenols, alkylated bisphenols, trisphenols, phenol-aldehyde novolac resins, haLogenated phenol-aldehyde novolac resins, alkylated phenol-aldehyde novolac resins, hydrocarbon-phenol resins, hydrocarbon-halogenated phenol resins, or hydrocarbon-alkylated phenol resins, or any combination thereof and the like. Even more preferable polyglycidyl ethers of polyaromatichydroxy compounds include, for example, the diglycidyl ethers of resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,l-bis(4-hydroxylphenyl)-l-phenyl ethane), bisphenol F, bisphenol K, tetrabromobispnenol A, phenol-formaldehyde novolac resins, alkyl substituted phenol-formaldehyde resins, phenol-hydroxybenzaldehyde 15 resins, cresol-hydroxvbenzaldehyde resins, dicyclopentadiene-phenol resins, dicyclopentadiene-substituted phenol resins tetramethylbiphenol, tetramethyl-tetrabromobiphenol, tetramethyltribromobiphenol, tetrachlorobisphenol A, tetrabromobisphenol A, any combination thereof and the like. Preferably the polyglycidyl ether of the polyaromatichydroxy compounds is a nominally diglycidyl ether of a polyaromatichydroxy compound, meaning that 25 the actual materials used are a mixture of compounds resulting from the process for preparation wherein the average number of glycidylether moieties per molecule approaches two. 20 30 Optionally the advanced flexibilized epoxy resins of this invention can contain the residue of a chain terminator. In practice a chain terminator is a material which has only one reactive moiety containing an active hydrogen atom. Such chain terminator functions C-39,462-F 20 21 to reduce the molecular weight of the proposed material and are well known in the art. An example of a preferable chain terminator is paratertiarybutyl phenol. 10 In the preferred embodiment wherein the polyaromatichydroxy compound is a nominally diaromatichydroxy compound, and the polyglycidyl ether of a polyaromatichydroxy compound is nominally a diglycidyl ether of a diaromatichydroxy compound, the advanced flexibilized resins of this invention correspond to formula 10: 10 / Oh / ( \ N / ICH-TCHCH-OArO-CH2CHTCH7-OArO-E ■ V ' 1 I / N iH 3 -|"CH2TCHCH2-OArO--^-CH2CHTCH2-3-CH2T CHCH2-OArO-j-CH2CHTCH2-OArO-E OH OH OH ^ OH 25 wherein B is independently in each occurrence R R ,-fUo^ , 30 E is independently in each occurrence a moiety according to one of the formulas C-39,462-F 21 22 -CH,-TCHCH, or \ / O 244 06! -CI I,-T-CI I-CI 1,-0 ArO-CI I,-CI I-T-CI 12-b{CI I,TCH-CH2-OArO-CH2-CI I-T-CHrOArO "I "I ^ * I I OH OH OH OH 25 t-CH,-T-CH-CH, \ / O b-1 d is independently in each occurrence a number of from 0 10 to 2; e is independently in each occurrence 0 or 1; and Ar, R, T, Z, X, a, b and c are as defined hereinbefore. 25 In one preferred embodiment of the invention, the flexibilized advanced epoxy resin are converted to flexibilized advanced epoxy cationic resins which have a charge density of from 0.2 to 0.6 milliequivalents of cationic charge per gram of resin. Such resins are 20 prepared by reacting the terminal glycidyl ether moieties with a nucleophile and thereafter converting the reaction product to cationic species. Nucleophiles useful for performing this reaction are well-known to those skilled in the art. Preferred nucleophiles are monobasic heteroaromatic nitrogen compounds, tetra(lower alkyl) thioureas, sulfides corresponding to formula 11: R6-S-R6 11 30 amines corresponding to formula 12: R7-f\j-R8 12 R8 or phosphines corresponding to formula 13: C-39,462-F 22 "TV _ ■ 23 R9-f>-R9 13 R9 3 wherein; R6 is independently in each occurrence lower alkyl, hydroxy lower alkyl or two of R& may combine as one 3 to 5 carbon atom alkylene radical thereby forming a neterocycloalkylene moiety; 10 R7 is independently in each occurrence hydrogen, hydroxyalkyl, lower alkyl, aralkyl or aryl; R8 is independently in each occurrence hydrogen, lower i_5 alkyl, hydroxy lower alkyl, the moiety —R10_N=C< X R11 20 or two of R8 may combine to form an alkylene radical having from 3 to 5 carbon atoms; R9 independently in each occurrence lower alkyl, hydroxy 25 lower alkyl or aryl; RlO is independently in each occurrence a C2-10 alkylene group; Rll is independently in each occurrence lower alkyl. Preferably the nucleophile is an amine, more preferably a primary or secondary amine. C-39,462-F 23 - Q 24 Representative nucleophilic compounds are pyridine, nicotinamide, quinoline, isoquinoline, tetramethyl thiourea, tetraethyl thiourea, 5 hydroxyethylmethyl sulfide, hydroxyethylethyl sulfide, dimethyl sulfide, diethyl sulfide, di-n-propyl sulfide, methyl-n-propyl sulfide, methylbutyl sulfide, dibutyl sulfide, dihydroxyethyl sulfide, bis-hydroxybutyl sulfide, trimethylene sulfide, thiacyclohexane, tetrahydrothiophene, dimethyl amine, diethyl amine, dibutyl amine, 2-(methylamino)ethanol, diethanolamine, N-methylpiperidine, N-ethylpyrrolidone, N-hydroxyethylpyrrolidine, trimethylphosphine, triethyl-phosphine, tri-n-butyl-phosphine, trimethylamine, triethylamine, tri-n-propylamine, tri-isobutylamine, hydroxyethyl-dimethylamine, butyldimethy1amine, trihydroxyethylamine, triphenylphosphorus, and N,N,N-dimethylphenethylamine; and the ketimine derivatives of 20 polyamines containing secondary and primary amino groups such as those produced by the reaction of diethylene triamine or N-aminoethylpiperazine with acetone, methyl ethyl ketone or methylisobutyl ketone. 25 In a preferred embodiment the nucleophile is a primary or secondary amine, the polyaromatichydroxy compound is a diaromatichydroxy compound, and the 30 polyglycidyl ether of a polyaromatichydroxy compound is a diglycidyl ether of a diaromatichydroxy compound, and such compounds preferably correspond to the following formula 14: C-39,462-F 24 25 ?h I 20 25 (qH2TCHCH2-OArO-CH2CHTCH-OArO-G 1 ( 3 —LCH2TCHCH:-OArO-4-CH2CHTCH2-3-CH2T CHCH2-OAr04-CH2CHTCH2-OArO-G/ \ I V i ! " i I \ O- OH OH OH wherein: 10 G is independently in each occurrence a moiety according to one of the formulas: —CbMOCH, —N *-(R7)(R8)i CH,TCHCH?-0-H * I ' A- ; ' 1 OH (R7)(R8)2 N-A- Qr 15 f \ _L^,. ■ ■ - - o-G) —OArO-CH2 j.HTCH-3-^-CH2T|;HCH2 OArO-CH2 CHTCH2-OArO-G| OH OH OH ^ 1 A- is the anion of an acid as described hereinafter; and Ar, B, R, R7, R8, T, Z, X, a, b, c, d and e are as described hereinbefore. The flexibilized advanced epoxy resins of this invention preferably exhibit a weight average molecular weight of 900 or greater, more preferably 1200 or greater, and most preferably 1500 or greater. The flexibilized advanced epoxy resins of this invention preferably have a molecular weight of 50,000 or less, 30 more preferably 30,000 or less, and most preferably 20,000 or less. The flexibilized advanced epoxy resins of this invention preferably have an epoxy equivalent weight (EEW) of 450 or greater, more preferably 600 or greater, and most preferably 800 or greater. The flexibilized advanced epoxy resins of this invention C-39,462-F 25 26 preferably have an EEW of 5,000 or less, more preferably 4,000 or less, and most preferably 3,000 or less. - The inventors have recognized that he reactivity of a polyglycidyl ether of a pol butylene glycol with a polyaromatichydroxy compound is much lower than the reactivity of a polyglycidyl ether or a polyaromatichydroxy compound with a polyaromatichydroxy 10 compound. Therefore, unless the process conditions are carefully chosen, it is difficult to efficiently incorporate the polyglycidyl of a polybutylene glycol into the internal structure of and advanced epoxy resin. The process of this invention involves first reacting "3 the glycidyl ether of a water or di- or tri- hydroxy substituted Ci-6 hydrocarbon initiated polybutylene glycol with the polyaromatichydroxy compound under conditions such that substantially all of the glycidyl 7q ether moieties on the polyglycidyl ether of the polybutylene glycol are reacted with aromatichydroxy groups. In the second step the reaction product is reacted with a polyglycidyl ether of a polyaromatichydroxy compound under conditions such that 25 the terminal aromatichydroxy moieties of the reaction product react with the glycidyl ether moieties of the polyglycidyl ether of the polyaromatichydroxy compound, such that the terminal groups of the flexibilized epoxy resin are primarily glycidyl ether moieties. ^ Optionally, additional polyaromatichydroxy compounds may be present in the second step to facilitate the further advancement of the flexibilized epoxy resin. If desired a known chain terminator may be present in the reaction mixture in small quantities. C-39,462-F 26 27 In the first step, the polyglycidyl ether of the polybutylene glycol is contacted with the polyaromatichydroxy compound neat, in the absence of solvent, or in the presence of an organic solvent which demonstrates low affinity for water. Such solvents include aromatic hydrocarbons, mixtures of aromatic hydrocarbons and alkanols, glycol ethers and ketones. It is advantageous to include epoxy resin advancement catalyst, such as compounds containing amine, phosphine, heterocyclic nitrogen, ammonium, phosphonium, arsonium, or sulfonium moieties. Preferred catalysts are the phosphonium compounds. In the embodiment where the catalyst is a phosphonium or an amine preferably 500 ppm (parts per million) or more of the catalyst is present, more preferably 700 ppm or more. Preferably such catalyst is present in amounts of 3,000 ppm or less, more preferably 2000 ppm or less. Thereafter the reaction mixture is heated until an exotherm begins, generally at from 140 to 150°C. Preferably, the temperature of the mixture is increased at a rate of from 1 to 2°C per minute until the exotherm begins. The temperature is maintained at levels at which the reaction continues, until the reaction is completed. In those embodiments wherein a phosphonium catalyst is used a reaction generally stops itself. Where other catalysts are used, the reaction may be quenched by cooling. The reaction time is dependent upon the concentration of catalyst, materials present, presence of solvent and the reactivity of materials. Preferably reaction times are 15 minutes or greater, more preferably 30 minutes or greater. Preferably reaction times are 4 hours or less, and more preferably 3 hours or less. In a preferred embodiment, the amount of polyaromatichydroxy compound contacted with the polyglycidyl ether of the C-39,462-F 27 28 polybutylene glycol is sufficient to react with all of the glycidyl ether moieties of the polyglycidyl ether of polybutylene glycol. Preferably two moles of polyaromatichydroxy material or greater is present per mole of polyglycidyl ether of polybutylene glycol. In some embodiments it may be advantageous to have a significant excess of poLyaromatichydroxy material where such material would be advantageous in further advancing the reaction product in the second step. Once the reaction is complete, the reaction product may be recovered from the reaction mixture, or alternatively and preferably the polyglycidyL ether of the polyaromatichydroxy compound is thereafter added to the reaction mixture and the second step of the reaction is 15 performed. 10 20 In the preferred embodiment where a diaromatichydroxy compound is reacted with the polyglycidyl ether of the polybutylene glycol based material the reaction product of the first step preferably corresponds to Formula 15: R R tjt1 \ CH2-T-(;-CH2-OArOH } 15 a 6H ' b wherein Z, T, R, Rl, Ar, a, and b are as hereinbefore 30 defined. 25 In the second step of the reaction, the reaction product of the first step is contacted with a polyglicyidyl ether of a polyaromatichydroxy compound, C-39,462-F 28 29 and additional polyaromatichydroxy compound and/or chain terminator. Preferably, the molar amount of poivglycidylether of a polyaromatichydroxy compound is present in a ratio of greater than 1.0 as compared to the moles of the above-mentioned reaction product of the 3 first step and more preferably 1.5 moles or greater. Thereafter, the mixture is heated until exotherm occurs. Optionally, catalyst for the advancement of epoxy resins may be present. Alternatively, a sufficient amount of ,q catalyst may be introduced in step 1, such that no further catalyst need to be added in the second step. The reactants in the second step may be reacted neat or in the presence of a solvent. Solvents which may be used are those which are typically used as solvents for epoxy 15 advancement reactions. A reaction in solvent may be advantageous wherein heat control is desired. The advancement reaction is preferably performed at a temperature of 130°C or above, as below 130°C the reaction time is too slow. Preferably the reaction is 9 Q performed at a temperature of 230°C or less, the polymer reacts to fast above such temperature and unwanted colors may be formed due to the presence of oxidated byproducts. More preferably the reaction temperature is 180°C or below. The temperature which may be used for the reaction depends on whether or not a solvent is used, and its nature. The reaction mixture is preferably heated at a rate such that the temperature increases from 1 to 2°C per minute until exotherm is achieved. 30 Thereafter elevated temperatures are maintained until the desired molecular weight and epoxy equivalent weights are reached. The polyepoxide advancement reaction is allowed to proceed for a time sufficient to result in substantially complete reaction, preferably 15 minutes or greater, more preferably 30 minutes or C-39,462-F 29 30 greater. Preferably the maximum reaction time is 10 hours or Less and more preferably 2 hours or less. The flexibilized advanced epoxy resins of this invention can thereafter be recovered and formulated for use in various coatings applications. The flexibilized 3 advanced epoxy resins of the invention may be recovered in a semi-solid or solid state by means well known in the art. The coating compositions which can incorporate ^ the flexibilized epoxy resins of this invention include powder coating compositions, food and beverage can coating compositions and ambient cure coatings useful in industrial maintenance applications. In those embodiments where the resin will be used in marine or industrial maintenance applications, powder, or food and beverage can coatings, the resin may be recovered and then converted to a form useful for such coatings. -,q In one preferred embodiment, the flexibilized advanced epoxy resins of this invention are converted to cationic resins for use in cathodic electrodeposition coatings by reacting at least some of the glycidylether moieties of the resin with a nucleophilic compound and 25 adding an organic acid and water at some point during the preparation. It is also possible to react at Least some of the glycidyl ether moieties with a nucleophile salt formed by prereacting the nucleophile with the organic acid. 30 Substantially any organic acid, especially a carboxylic acid, can be used in the conversion reaction to form onium salts so long as the acid is sufficiently strong to promote the reaction between the nucleophilic C-39,462-F 30 4 31 10 compound and the glycidyl ether moieties of the resin. In the case of the salts formed by addition of acid to a secondary amine/epoxy resin reaction product, the acid should be sufficiently strong to protonate the resultant tertiary amine product to the extent desired. Monobasic acids are normally preferred (H+A~). Preferable organic acids include, for example, alkanoic acids having from 1 to 4 carbon atoms (e.g., acetic acid, propionic acid, etc.), alkenoic acids having up to 5 carbon atoms (e.g., acrylic acid, methacrylic acid, etc) hydroxy-functional carboxylic acids (e.g., glycolic acid, lactic acid, etc.) and organic sulfonic acids (e.g., methanesulfonic acid), and the like. Presently preferred acids are lower alkanoic acids of 1 to 4 carbon atoms with lactic acid 15 and acetic acid being most preferred. The anion can be exchanged, or course, by conventional anion exchange techniques. See, for example, US Patent 3,959,106 at column 19. Preferable anions are chloride, bromide, bisulfate, bicarbonate, nitrate, dihydrogen phosphate, lactate and alkanoates of 1-4 carbon atoms. Acetate and lactate are the most preferred anions. 20 25 30 The conversion reaction to form cationic resins is normally conducted by blending the reactants together. Good results can be achieved by using substantially stoichiometric amounts of reactants although a slight excess or deficiency of the epoxy-containing resin or the nucleophilic compounds can be used. With weak acids, useful ratios of the reactants range from 0.5 to 1.0 equivalent of nucleophilic compounds per glycidyl ether moiety of the resin and for organic acids from 0.5 to 1.1 equivalents of organic acid per glycidyl ether moiety. These ratios, when C-39,462-F 31 32 J combined with the preferred epoxide content resins described above, provide the desired range of cationic charge density required to produce a stable dispersion of the coating composition in water. With still weaker acids a slight excess of acid is preferred to maximize 3 the yield of onium salts. When the nucleophilic compound is a secondary amine, the amine-epoxy reaction can be conducted first, followed by addition of the organic acid to form the salt and thus produce the cationic form ,q of the resin. For the onium-forming reactions, the amount of water present can be varied so long as there is sufficient acid and water present to stabilize the cationic salt formed during the course of the reaction, preferably water is present in amounts of from 5 to 30 moles per epoxy equivalent. It is advantageous to include minor amounts of organic solvents in the 20 reaction mixture, the presence of which facilitates contact of the reactants and promotes the reaction rate. One preferred class solvents are the monoalkyl ethers of the C2-4 alkylene glycols, which includes the monomethyl ether of ethylene glycol, the monobutyl ether of ethylene glycol, etc. When the desired degree of reaction is reached, any excess nucleophilic compound can be removed by standard methods, e.g., dialysis, vacuum stripping and steam distillation. 30 The cationic, advanced epoxy resins of this invention in the form of aqueous dispersions are useful as coating compositions, especially when applied by electrodeposition. The coating compositions containing the cationic resins of this invention as the sole ~ C-39,462-F 32 33 resinous component could be used but it is preferred to include crosslinking agents in the coating composition, so that the coated films, when cured at elevated temperatures, will be crosslinked and exhibit improved film properties. Materials suitable for use as crosslinking agents are those known to react with hydroxyl groups or amino protons; and include blocked polyisocyanates; amine-aldehyde resins such as melamine-formaldehvde, urea-formaldehyde, benzogucinine-formaledyde, and their alkylated analogs; polyester resins, and phenol-aldehyde resins. Preferred crosslinking agents are the blocked polyisocyanates which, at elevated temperatures, deblock and form isocyanate groups which react with the hydroxyl groups of the resin to crosslink the coating. Such crosslinkers are prepared by reaction of the polyisocyanate with a monofunctional active-hydrogen compound. Examples of polyisocyanates and isocyanate-functional prepolymers derived from polyisocyanates and polyols using excess isocyanate groups suitable for preparation of the crosslinking agent are described in US Patent 3,959,106 to Bosso, et al., in Column 15, lines 1-57. The blocked polyisocyanate crosslinking agents are incorporated into the coating composition at levels corresponding to from 0.2 to 2.0 blocked isocyanate groups per hydroxyl group of the cationic resin. The preferred level is from 0.5 to 1.0 blocked isocyanate group per resin hydroxyl group. A catalyst optionally may be included in the coating composition to provide faster or more complete curing of the coating. Preferable catalysts for the various classes of crosslinking agents are known to those skilled in the C-39,462-F 33 10 34 art. For the coating compositions using the blocked polyisocyanates as crosslinking agents, preferable catalysts include dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin oxide, stannous octanoate, and other urethane-forming catalysts known in the art. Preferably the catalyst is used in amounts from 0.1 to 3 weight percent of binder solids. Unpigmented coating compositions are prepared by blending the cationic resinous product with the crosslinking agent and optionally any additives such as catalysts, solvents, surfactants, flow modifiers, and defoamers. This mixture is then dispersed in water by any of the known methods. The solids content of the aqueous dispersion is usually from 5 to 30 percent by weight, and preferably from 10 15 to 25 percent by weight for application by electrodeposition. Pigmented coating compositions are prepared by 20 adding a concentrated dispersion of pigments and extenders to the unpigmented coating compositions. This pigment dispersion is prepared by grinding the pigments together with a suitable pigment grinding vehicle in a suitable mill as known in the art. Pigments and extenders known in the art are useful in these coatings, and include pigments which increase the corrosion resistance of the coatings. Examples of useful pigments or extenders include titanium dioxide, talc, clay, lead oxide, lead silicates, lead chromates, carbon black, strontium chromate, and barium sulfate. 25 30 The pH and/or conductivity of the coating compositions may be adjusted to desired levels by the addition of compatible acids, bases, and/or electrolytes C-39,462-F 34 L 35 known in the art. Other additives such as solvents, surfactants, defoamers, anti-oxidants, bactericides, etc. may also be added to modify or optimize properties of the compositions or the coating in accordance with practices known to those skilled in the art. 5 The coating compositions of the invention may be applied by cathodic electrodeposition, wherein the article to be coated is immersed in the coating i a composition as the cathode, with a suitable anode in contact with the coating composition. When sufficient voltage is applied, a film of the coating deposits on the cathode and adheres to the article to be coated. Voltage applied is preferably from 10 to 1,000 volts, more preferably from 50 to 500 volts. The film thickness achieved increases with increasing voltage. Thicker films are achieved by incorporation of the diglycidyl ether of polybutylene glycol into the backbone of the 20 cationic resins of the invention. Control over the final thickness may be excercised by adjusting the amount of that component used. The voltage is applied for between a few seconds to several minutes, preferably from two minutes over which time the current usually decreases as ''S . . . a resistive film is deposited. Any electrically conductive substrate may be coated in this fashion, especially metals such as steel and aluminium. Other aspects of the electrodeposition process are -jq conventional. After deposition, the article is removed from the bath and rinsed with water to remove that coating composition which does not adhere. The uncured coating on the article is cured by heating at elevated temperatures, preferably ranging from 100° to 200°C, for periods of preferably from 1 to 60 minutes. C-39,462-F 35 36 In another embodiment the flexibilized advanced epoxy resins may be flaked or ground according to known processes and combined with epoxy curing agents and exposed to conditions such that continuous films are formed, without conversion to cationic species. Processes for preparing such powder coatings are generally well known to those skilled in the art. 1° In another embodiment the flexibilized advanced epoxy resins of this invention can be used in solvent coatings. In such an embodiment the flexibilized advanced epoxy resins and a curing agent can be 15 dissolved in a solvent and such mixture can be coated onto a substrate and exposed to curing conditions. Preferred solvents are alkyl substituted benzenes, ketones, lower alkanols, glycol ethers, chlorinated alkanes, and dimethyl formamide. The preferred solids 9Q level is from 25 to 80 % by weight; and preferably from 30 to 60 % by weight. Generally curing conditions comprise exposing the coated substituted to temperatures from 20 to 250°C under conditions such that the solvents can be removed from the coating. The flexibilized advanced epoxy resins of this invention are cured with known curing agents for epoxy 3Q resins. In preparing coatings the flexiblized epoxy resin compositions are contacted with curing agents and the mixture is applied in a known manner to a substrate such that the flexibilized advanced epoxy resins are cured to form coatings. Curing agents useful in this invention are those compounds known to the skilled C-39,462-F 36 37 artisan to react with polyepoxides or advanced epoxy resins to form hardened final products and which function to cure the epoxy resin. 10 The polyhydroxy compounds described hereinbefore wherein the hydroxy moieties are bound to aromatic moieties are among suitable curing agents. The novolac based compounds and the bisphenolic compounds are the preferred polyhydroxy compounds for use as curing agents. Examples of other preferable curing agents include the polvbasic acids and their anhydrides; other types of acids containing sulfur, nitrogen, phosphorus or halogens; soluble adducts of amines and polyepoxides and their salts, such as described in US 2.651,589 and US 2,640,037; acetone soluble reaction products of polyamines and monoepoxides; the acetone soluble reaction products of polyamines with unsaturated nitriles; imidazoline compounds obtained by reacting 20 monocarboyxlic acids with polyamines; sulfur and/or phosphorus-containing polyamines obtained by reacting a mercaptan or phosphine containing active hydrogen with an epoxide halide to form a halohydrin, dehydrochlorinating and then reacting the resulting product with a polyamine; soluble reaction product of polyamines with acrvlate; and many other types of reaction products of the amines; boron trifluoride and complexes of boron trifluoride with amines, ethers, phenols and the like; Friedel-Crafts metal salts, such as aluminum chloride, zinc chloride, and other salts, such as zinc fluorborate, magnesium perchlorate and zinc fluosilicate; inorganic acids such as phosphoric acid and partial esters thereof including n-butyl orthothiophosphate, diethyl orthophosphate and 25 30 C-39,462-F 37 38 hexaethyltetraphosphate; polyamides containing active amino and/or carboxyl groups, and preferably chose containing a plurality of amino hydrogen atoms, especially preferred polyamides are those derived from the aliphatic polyamides containing no more than 12 D carbon atoms and polymeric fatty acids obtained by dimerizing and/or trimerizing ethylenically unsaturated fatty acids containing up to 25 carbon atoms; and melamine reaction products containing methylol substituents. Preferred classes of curing agents are the polyamines and amides. Such preferred curing agents include aliphatic polyamines, polyglycoldiamines, polyoxypropylene diamines, polyoxypropylenetriamines, amidoamines, imidazolines, reactive polyamides, ketimines, aralipnatic polyamines (i.e. xylylenediamine), cycloaliphatic amines (i.e. 20 isphoronediamine or diaminocyclohexane) menthane diamine, 3,3-dimethy1-4,4-diamino-dieyelohexylmethane, heterocyclic amines (aminoethyl piperazine), aromatic polyamines, (methylene dianiline), diamino diphenyl sulfone, mannich base, phenalkamine, N,N1N11-tris(6- °5 aminohexvl) melamine, and the like. Most preferred are cyanamide, dicyandiamide, and its derivatives, diaminodiphenyl sulphone and methylene dianiline. The flexibilized advanced epoxy resin compositions of this invention are contacted with sufficient curing agents to cure the resin. Preferably the ratio of epoxy (glycidyl ether) equivalents to equivalents of curing agent is from 0.5 : 1 to 2 : 1; more preferably from 0.6 : 1.4 to 1.4 : 0.6; even more C-39,462-F 38 39 preferably from 0.8 : 1.2 to 1.2 : 0.8 and most preferably from 0.9 : 1.1 to 1.1 : 0.9. The coatings of this invention demonstrate excellent adhesion, resistance to cathodic disbondtnent, - excellent flexibility and impact resistance, good compatibility with a wide variety of resinous binders, such as acrylics, alkyds, polyesters as well as curing agents like polyamines, melamine or phenol resins. The following examples are included for ^ illustrative purposes only and do not limit the scope of the claims. Unless otherwise stated all parts and percentages are by weight. ^ EXAMPLE 1 - Reaction of polypropylene glycol diglycidyl ether, bisphenol A and diglycidyl ether of bisphenol A. Not an example of the invention. 20 To a to a 5 1 glass reactor are charged 1550.4 g of a diglycidyl ether of bisphenol A having an EEW of 187.0 (8.33 epoxy eq), 618.0 g of a diglycidyl ether of polypropylene glycol (EEW of 334.0) prepared from a 25 polypropylene glycol having a molecular weight of 425 (1.85 epoxy equivalents) and 831.6 g of bisphenol A (7.29 eq of phenolic hydroxyl). The mixture is heated to 100°C and 2.9 g of alkyltriphenyl phosphonium catalyst is added. The reactor is slowly heated to 140°C. At 30 140°C the reaction mixture exotherms and the temperature rises to 160°C. The temperature is maintained at 160°C for 60 minutes at which time a sample of the reaction mixture is taken which demonstrates an EEW of greater than 1000. The reaction is quenched by cooling. The resulting resin is crushed and stored. The final epoxy equivalent weight is 1059. C-39,462-F 39 40 The solid resin is converted into a water-dispersed form usable for the formulation of cathodic electrodeposition primers by following procedure. In a reactor 620 g of the solid resin is dissolved in a mixture of 34.4 g xylene and 34.4 g Dowanol* ?Ph glycol D ether, the phenyl ether of propylene glycol at a temperature of 110°C. 467.4 g of a 70 wt % solution of blocked polymeric methylene diisocyanate crosslinker in methyl isobutyl ketone is blended with the resin solution. Then 40.7 g of a 73 wt % solution in methylisobutylketone of the diketimine of methylisobutylketone and diethylenetriamine is added, followed by 33.1 g of methvlethanolamine. The reactor is cooled to keep the reaction temperature from rising over 15 110°C. A temperature of 1100C is maintained for 60 minutes. Then 38.3 g of Dowanol* PPh glycol ether is added to the reactor. A second reactor is now prepared containing a mixture of a 1306 g of deionized water, 39.3 g of lactic acid (0.31 eq. of acid) as well as 17.2 20 g of a mixture of suitable cationic surfactant and defoamer. Under strong stirring the hot resin mixture is slowly poured into the second reactor, whereby a low viscosity dispersion is obtained. The dispersion is 25 diluted further by the addition of 637.0 g of deionized water. The dispersion is heated to 65°C, after which the volatile organic solvents are stripped off over 2 hours by distillation at a reduced pressure of 250 mbar. The solids content of the dispersion, after 1 hour drying at 30 150°C, is determined to be 36.40 %. The dispersion is mixed with a commercially available pigment paste and diluted by addition of deionized water so that the final * Trademark of The Dow Chemical Company C-39,462-F 40 41 pigmented dispersion has a 0.3 : 1 ratio of pigment to binder at a solids content of 20 wt %. EXAMPLE 2 - Reaction of diglycidyl ether of 5 polypropylene glycol with bisphenol A and subsequent reaction of the product with diglycidyl ether of bisphenol A Not an Example of the Invention. 10 To a reactor similar to the one described in Example 1 is charged 618.1 g of the diglycidyl ether of polypropylene glycol described in Example 1 and 831.6 g of bisphenol A (7.24 eq of phenolic hydroxyl). The mixture is heated to 100°C and 2.9 g of alkyltriphenylphosphonium catalyst is added. The reactor is slowly heated to 150°C (1 to 2°C per minute). At 150°C an exotherm begins and the reaction temperature 20 increases to 160°C. The temperature is maintained at 160°C until the weight percentage of epoxy in the mixture is less than 0.1 parts by weight; about 60 minutes. To the reaction mixture is added 1550.4 g of the diglycidyl ether of bisphenol A described in Example n 5 1 (8.33 epoxy equivalents). The temperature drops to !10°C as a result of this addition. The mixture is mixed for 5 minutes and then the temperature is slowly raised by heating (1 to 2°C per minute). At 140°C an exotherm begins and the temperature rises to 170°C. The temperature is reduced with cooling to 160°C at which temperature the reaction mixture is maintained until a sample removed shows the resin has an epoxy equivalent weight of more than 1000. The reaction is quenched by cooling, and the resulting solid resin has an EEW of C-39,462-F 41 42 1099. An aqueous dispersion is prepared as described in Example 1, the amount of amine added is 95 % of the epoxy equivalents, and the amount of lactic acid is adjusted to reach the same neutralization level. 5 EXAMPLE 3 - Reaction of diglycidyl ether of polypropylene glycol with bisphenol A and subsequent reaction of the product with diglycidyl ether of bisphenol A 10 Not an Example of the Invention. Example 2 is repeated using 620.0 g of the diglycidyl ether of polypropylene glycol (EEW 317.7) prepared from a polypropylene glycol of MW 390, 571.0 g of bisphenol A and 2.9 g of alkyltriphenylphosphonium catalyst. The mixture is heated to 100°C. The reactor is then slowly heated to 150°C (1 to 2°C per minute).To the 20 reaction mixture is added 1543.8 g of the diglycidyl ether of bisphenol A described in Example 1 (8.33 epoxy equivalents). The temperature drops to 110°C as a result of this addition. The mixture is mixed for 5 minutes and then the temperature is slowly raised by heating (1 to 25 2°C per minute). At 140°C an exotherm begins and the temperature rises to 170°C. The temperature is reduced with cooling to 160°C at which temperature the reaction mixture is maintained until a sample removed shows the 2q resin has an epoxy equivalent weight of more than 1000. The reaction is quenched by cooling, and the resulting solid resin is crushed and stored. The EEW is 1082. An aqueous dispersion is prepared as described in Examples 1 and 2. C-39,462-F 42 4 43 EXAMPLE 4 - Reaction of diglycidyl ether of polybutylene glycol and bisphenol A and subsequent reaction with the diglycidyl ether of bisphenol A Example 3 is repeated with 412.2 g of a - diglycidyl ether of a polybutylene glycol (EEW 250.0), wherein the polybutylene glycol MW (number average) is 300; 583.8 g of bisphenol A, and 2.0 g of catalyst as described in Example 1. It takes about 90 minuxtes until the weight percentage of epoxy in the mixture is less 10 than 0.1. To the reactor is added 1004.9 g of the liquid epoxy resin described in Example 1. The resulting solid resin has ane EEW of 1090. A water dispersion is prepared as described in Examples 1 and 2. 15 EXAMPLE 5 - Reaction of diglycidyl ether of polybutylene glycol and bisphenol A and subsequent reaction with diglycidyl bisphenol A Example 3 is repeated with 412.2 g of a diglycidyl ether of a polybutylene glycol (EEW 367.0), wherein the MW (number average) of the polybutylene glycol precursor is 550; 546.5 g of bisphenol A, and 2.0 g of catalyst as described in Example 1. It takes about 25 60 minutes until the weight percentage of epoxy in the mixture is less than 0.1. To the reactor is added 1042.2 g of the liquid epoxy resin described in Example 1. The EEW of the resulting resin is 1087. An aqueous dispersion is prepared as described in Examples 1 and 2. 20 30 The dispersions of Examples 1 to 5 are tested for pH and conductivity. The results are compiled in Table I. C-39,462--F 43 44 Table I Example Oxide Reaction Procedure pH Conductivity uS/cm** l* propylene oxide 1 step 6.5 1490 2* propylene oxide 2 step 6.2 1360 3* propylene oxide 2 step 6.0 1470 4 butylene oxide 2 step 6.3 1154 5 butylene oxide 2 step 6.2 1254 * Not an example of the invention ** Microsiemens / centimeter EXAMPLES 2 to 5 - Cathodic Deposition of Coatings and Testing of Properties 15 Dispersions prepared in Examples 2 to 5 are separately deposited on Bonder 26 phosphatized steel panels by electrodeposition, rinsed in deionized water and baked at 175°C for 20 minutes. Deposition 20 conditions are chosen such that the coating has a thickness of 25 microns. The Erichsen Indentation test is performed to a "first crack" endpoint. The Salt Bath corrosion test conditions are 500 hours of immersion in a 5 percent sodium chloride in water solution at 55°C. The results are compiled in Table II. EXAMPLE 6 - Reaction of Diglycidyl ether of Bisphenol A, diclycidyl ether of polypropylene glycol, and 30 Bisphenol A Not an example of the invention The following-amounts of raw materials are charged into a 1 liter glass reactor: 382.7 g D.E.R.* 331 epoxy resin (EEW= 186.9), 200 g of D.E.R.* 732 jjpoxy C-39,462-F 44 45 Table II Example Erichsen mm Salt Bath Immersion mm Creep Rev. Impact in.lbs 2 6.2 0.5-1.0 < 5 3 5.7 < 0.5 - 4 7.6 < 0.5 10 5 7.5 < 0.5 20 10 resin, the diglycidyl ether of a polypropylene glycol, (EEW= 318.5) and 217.3 g of Bisphenol A. The mixture is heated under stirring and a nitrogen purge to 90°C and then 0.71 g of a trialkylphosphonium catalyst is added. The temperature is gradually increased. At 140°C the exotherm begins and the temperature increases to 180°C. The temperature is then decreased with cooling to 170°C and maintained for 45 minutes, until a sample of the 2o reactor contents shows an EEW of 1050. The resin is cooled, crushed and stored. The resulting resin is converted into an 25 aqueous dispersion using the procedure described in Example 1, with the exceptions that the crosslinker is as described in US Patent 4,104,147, more particularly 70 wt % solution in MIBK of an 3:1:3 adduct (based on molar quantities) of toluenediisocyanate, 30 trimethylolpropane and ethylhexanol. Additionally, 10 g of dibutyltindilaurate curing catalyst is added to the resin crosslinker blend, just before dispersing it into water. C-39,462-F 45 46 After stripping, the dispersion is diluted to 20 wt 1 solids and used for eleccrodepositing an unpigmented coating unto Bonder 26 panels and unto degreased untreated steel panels. The coatings are cured for 20 minutes at 190°C. Deposition conditions are D chosen in such a way that the final film thickness of the cured films is 20 urn. EXAMPLE 7 - Reaction of Bisphenol A with diglycidyl ^ ether of polypropylene glycol, and subsequent reaction with 3isphenol A diglycidyl ether. Not an example of the invention The following amounts of raw materials are ^ charged into a 11 glass reactor: 200 g of D.E.R.* 732 epoxy resin, the diglycidylether of polypropyleneglycol, (EEW= 318.5) and 217.3 g of bisphenol A. The mixture is heated under stirring and nitrogen purging to 90°C after 2Q which 0.71 g of a trialkylphosphonium catalyst is added. The reaction mixture is gradually heated to 170°C, and maintained for 50 minutes until analysis of a sample of the reaction mixture shows an epoxy content less than 0.1 wt %. 387.2 g of D.E.R.* 331 epoxy resin (EEW= 25 186.9) are added, causing a temperature drop to 110°C, after which the mixture is reheated to 130°C. The exothermic effect of the continuing reaction raises the temperature to 170°C. The reaction is continued at that temperature for 20 minutes until analysis of the resin 30 gives an EEW value of 1072. The resin is cooled, crushed and stored. The conversion into an aqueous dispersion, the electrodeposition of the resulting clear coating and its C-39,462-F 46 47 curing are performed in the same way as described in Example 6. EXAMPLE 8 - Reaction of diglycidyl ether of Bisphenol A 5 diglycidyl ether of polypropylene glycol and Bisphenol A Not an example of the invention Using the procedure as described in Example 5 a resin is prepared. The reactor is charged with 389.2 g 10 of D.E.R.* 331 epoxy resin, 200.0 g of the diglycidylether of a polybutylene glycol (EEW= 368.12) and 210.8 g of bisphenol A. The resulting resin has an EEW of 1050. 15 Conversion into an aqueous dispersion, electrodeposition and curing are performed in the same manner as described in Example 6, except for the amount of neutralizing acid, which is 5 % higher. 20 EXAMPLE 9 Reaction of Bisphenol A with diglycidyl ether of polybutylene glycol and subsequent reaction with diglycidyl ether of Bisphenol A 25 Using the procedure described in Example 6, 200 g of the diglycidylether of a polybutyleneglycol (EEW= 368.1) and 210.8 g of bisphenol A are charged into the ^ reactor and the reaction proceeds. In the later stage of the reaction 389.2 g of D.E.R.* 331 epoxy resin is added. The resulting resin has an EEW of 1054. Conversion into an aqueous dispersion, electrodeposition and curing are performed in the same way as described in C-39,462-F 47 48 ExampLe 6, except for the amount of neutralizing acid which is 5 % higher. Results of pH and conductivities of the clear 5 dispersions of Examples 6-9 at 20 wt % solids are listed in Table III. Results of reverse impact, Erichsen Indentation, Salt Bath immersion test and salt spray are also listed. The salt spray test is performed according to ASTM 3 117 for 300 hours on degreased untreated steel ^ panels coated with the cured panels. Tests performed on the cured clear coatings are shown in Table IV. Table III 20 25 30 Example Oxide Type Reaction Procedure pH Conductivity uS**/cm 6* propylene oxide 1 step 6.6 1790 7* propylene oxide 2 step 6.4 1850 8* butylene oxide 1 step 6.2 1660 9 butylene oxide 2 step 6.0 1484 Not an example of the invention ** Microsiemens/centimeter Table IV Exam pie Rev. Impact lbs.in Erichsen mm Salt Bath Immersion mm Salt Spray mm 6* 116 8.8 - 3.2 7* > 160 9.1 2.0 4.5 8* 100 8.7 - 3.5 9 > 160 9.2 1.0 2.0 * Not an example of the invention C-39,462-F 48 EXAMPLE 10 - Reaction of diglycidyl ether of polybutylene glycol with bisphenol A and subsequent reaction of the product with diglycidyl ether of bisphenol A and additional bisphenol A. 325 g (0.897 epoxy eq) of the diglycidyl ether of a 550 Mw polybutylene glycol and 408.5 g of bispenol A (3.583 eq of phenolic OH) are charged to a 5 liter reactor. A gentle nitrogen purge is started over the contents and the temperature is raised at a rate between 10 1 and 2 degrees C per minute while contents are stirred. When the reactor temperature reaches 120 C, 1.1 g of alkyltriphenyl phosphonium catalyst are added. Heating of the reactor is continued until a mild exotherm is observed to begin at around 150 C, at which time the external heating is discontinued. Once the exotherm finishes and the temperature returns again to 160 C, 3,240.1 g of a diglycidyl ether of bisphenol A having an EEW of 178 and an additional 1026.4 grams of bisphenol A are charged to the reactor. The temperature is again raised at a rate of between 1 and 2 degrees C per minute. At 100 C, and an additional 2.4 grams of alkyltriphenyl phosphonium catalyst are added. Heating is continued until the beginning of an exotherm is 25 observed. At this point the external heating is again discontinued. After exotherm cool-down, and flaking, the epoxy is analyzed and found to have an EEW of 759.7, a Metier softening point of 89.4 C, and a melt viscosity of 1.81 Pa.s at 150 C. 15 20 30 EXAMPLE 11 - Preparation, application and testing of a powder coating 840.4 grams of the flaked resin of EXAMPLE 10, 259.6 grams of D.E.H. 81 (commercially available C-39,462-F 49 50 phenolic OH functional hardener commonly used in pipe and functional powder coatings), 600 grams of Ti02, 200 grams of BaS04, and 100 grams of CaC03 are premixed mechanically in a lab mixer for 3 minutes at 600 RPM. This dry mix is then completely melt- homogenized by 3 feeding it through a ZSK 30 twin screw laboratory extruder at a temperature of 90 C and a screw speed of 300 RPM. The extrudate is cooled by passing it between two water cooled rolls and the resulting sheet is then jq flaked. The flakes are ground on a lab grinder until 100% will pass through a 100 micron screen. This final powder is bagged and kept cool and dry. 6 mm thick cold rolled steel panels are cut to nominal dimensions of 150 by 70 mm. The finished test ^ panels are degreased with acetone, glass blasted to an average profile of 10 microns, and promptly placed in a circulating air oven which has been set to 235 C. After preheating for 20 minutes, the panels are removed from 9q the oven and hung in a spray booth. The panels are electrostatically sprayed to an estimated thickness of 350 microns with the powder coating. After coating the panels are returned to the 235 degree oven for a 1 minute post cure, after which they are quenched by 25 immersion in cold water. The resulting coatings are hard and glossy. The flexibility of the coating is tested by bending the coated panels around an 18 mm diameter 2q mandrel in accordance with DIN 35571 flexibility test. 10 panels prepared as described and at an average coating thickness of 347 microns are found to toLerate a 36.5 degree flex before cracking. This is considered to be excellent flexibility. C-39,462-F 50 51 EXAMPLE 12 - Reaction of diglycidyl ether of polybutylene glycol with bisphenol A and subsequent reaction of the product with diglycidyl ether of bisphenol A. - 404.1 grams (1.609 epoxy eq) of the diglycdyl ether of the 330 Mw polybutylene glycol and 494.6 grams of bisphenol A (4.338 phenolic OH eq) are charged to a 2 liter reactor. A gentle nitrogen purge is started over the contents and the temperature is raised at a rate 10 between 1 and 2 degrees C per minute while contents are stirred. When the reactor temperature reaches 120 C, 1 gram of alkyltriphenyl phosphonium catalyst is added. Heating of the reactor is continued until a mild exotherm is observed to begin at around 150 C, at which time the external heating is discontinued. Once the exotherm finishes and the temperature returns again to 160 C, 601.4 g (3.36 epoxy eq) of diglycidyl ether of bisphenol A with EEW of 178.6 are charged to the 7q reactor. The reactor is again heated at a rate of 1 to 2 degrees per minute until the temperature reaches 120 C at which point an additional 1.65 grams of alkytriphenyl phosphonium catalyst are added. Heating of the reactor is continued until an exotherm is observed at around 150 25 degrees. At this point the external heating is discontinued until the reactor temperature falls again to 150 C. Reactor is then maintained at 150 until the EEW is found to exceed 2800. The advanced resin is poured from the reactor into an aluminum foil tray and allowed to cool to room temperature. The Metier Softening Point is determined to be 104.1 C and the solution viscosity at 40 wt % solids in diethylene glycol monobutyl ether is measured to be 1914 cSt. 30 C-39,462-F 51 52 EXAMPLE 13 - Formulation, application, and testing as a can coating 80 grams of the advanced resin of EXAMPLE 12 are dissolved in 150 grams of a solvent blend consisting - of 50 parts Dowanol PMA, 10 parts of 2-butanol and 40 parts of Solvesso 100. 10 grams (solids) each of Phenodur PR 285 and Bakelite 100 (commercial phenolic resole crosslinkers) are added to the advanced resin solution. 1 gram (solid) of phosphoric acid is added to 10 accelerate the cure. The formulation is allowed to age for 24 hours at 40 C and is then reduced with the solvent blend described above until a ASTM D445 viscosity of 250 mPa.s is reached. The solids content is measured to be 38 wt %. 15 The formulation is applied using a wire wrapped draw down rod to a 0.235 mm thick sheets of Ancrolyt tin free steel and Androlyt tin plate (both available from Rasselstein AG) which have been degreased by rinsing 20 with acetone. A wet application of between 20 to 40 microns is chosen such that dry film thickness of 5 to 6 microns is obtained. The coated tin plate panels are placed in a circulating air oven preheated to 200 C for a cure time of 10 minutes. The coated tin free steel 9 5 panels are cure at 280 for 28 seconds. To test the performance of the coatings, 2 cm high asymmetric cans with 5, 10, 15, and 20 mm radius corners were drawn from the coated tin free steel and 30 tin plate sheets. In each case, perfect coating integrity on all corners and edges is maintained throughout the drawing process. The drawn cans are further tested by exposing them to water at 129 C. The exposure time is 30 minutes for the tin plate cans and 90 minutes for the tin free steel cans. In each case, C-39,462-F 52 </div>

Claims

<div class="application article clearfix printTableText" id="claims"> 53 the integrity of the coating is maintained during the exposure and no blushing or blistering is observed. 15 20 7-'' ■« < .! .« ' ■■ ■ If , I - 1: . -i'/t li ' ' C-39,462-F 53 54 WHAT fjfWE CLAIM IS: -PATENT CLAIMS"?

1. Flexibilized epoxy resin comprising the residue of A. one or more polyglycidyl ethers of a water or di- or trihydroxy substituted Ci-6 hydrocarbon 3 initiated polybutylene glycol; B. one or more polyaromatichydroxy compounds; and 10 C. one or more polyglycidyl ethers of polyaromatichydroxy compounds; wherein substantially all of the glycidyl ether moieties of polybutylene glycol are bound to the polyaromatichydroxy 15 compounds through the reaction product of the glycidyl ether moieties with the aromatichydroxy moieties; each polyaromatichydroxy compound is bound to at least one polyglycidyl ether of polybutylene glycol or at 20 least one polyglycidyl ether of polyaromatichydroxy compound through the reaction product of an aromatichydroxy moiety and glycidyl ether moiety; each residue of polyglycidyl ether of polyaromatichydroxy compound is bound to at least one residue of 25 C-39,462-F 54 ^44 polyaromatichydroxy compound through the reaction product of a glycidyl ether x.oiety and an aromatichydroxy moiety; wherein the mole ratio of polyaromatichydroxy compound 5 to polyglycidyl ether of polybutylene glycol is two "of <. and sufficient polyglycidyl ether of polyaromatichydroxy compound is present in the resin such that the terminal moieties of the resin are glycidyl ether moieties from the polyglycidyl ethers of ^ polyaromatichydroxy compounds.

2. Flexibilized epoxy resin compositions 15 according to Claim 1 wherein the epoxy resin contains at least 5 percent by weight of polyglycidyl ethers of polybutylene glycol. the polyaromatichydroxy compound corresponds to the 30 formula: 20

3. Flexibilized epoxy resin compositions according to Claim 2 wherein the glycidyl ether of a polybutylene glycol corresponds to the formula: 25 C-39,462-F 55 56 and the polyglycidyl ether of a polyaromatichydroxy compound corresponds to the formula: Ar CH2-T-CHCH2y where in: Ar is independently in each occurrence a hydrocarbon 10 moiety containing one or more aromatic rings, or a hydrocarbon moiety containing one or more aromatic rings and one or more heteroatoms of oxygen, nitrogen, sulfur or halogen; 15 R is independently in each occurrence hydrogen, methyl or ethyl with the proviso that for each unit either both of R are methyl or one R is ethyl and the other is hydrogen; 25 T is independently in each occurrence a direct bond or the moiety R R 20 30 v.n2v.i Z is independently in each occurrence oxygen or C-39,462-F 56 I 3 / 244069 Z> X{°h X is independently in each occurrence a Ci-6 alkyl moiety; R1 is independently in each occurrence hydrogen or a 10 C1-4 alkyl moiety; a is independently in each occurrence a positive real number of 1 or greater; b is independently in each occurrence 2 or 3; c is independently in each occurrence a positive real number of greater than 1; 20 25 30 with the proviso that the hydroxy moieties of the polyaromatichydroxy compounds and the glycidyl ether moieties of the polyglycidyl ethers of polyaromatichydroxy compounds are bound to aromatic rings. A.

Flexibilized epoxy resins according to Claim 3 wherein the resins comprise compounds corresponding to the formula C-39,A62-F 57 c r i V 2440 CH \ CH2TCHCHrOArO-CH2CHTCH-OArO-E / I 3—rCH:TCHCH2-°Ar0—|-CH2CHTCH2-3-CH2TCHCHrOArCH-CH:CHTCH2-OArO-EJ V M OH OH OH 1U wherein: 15 Ar is independently in each occurrence a hydrocarbon moiety containing one or more aromatic rings, or a hydrocarbon moiety containing one or more aromatic rings and one or more heteroatoms of oxygen, nitrogen, sulfur or halogen; B is 20 25 E is independently in each occurrence a moiety according to one of the formulas -CH2-TCHCH2 \/ O or -CH2-T~CH-CH2-OAtO-CH2-CH-T-CH2-Bt CH2TCH-CH2-OArO-CH2-CH-T-CH2-OArO I 1^1 I OH OH OH OH c CH2-T-CH-CH2 \ / 0 b-1 C-39,462-F 58 244069 R is independently in each occurrence hydrogen, methyl or ethyl with the proviso that for each R R :h<[ho^— unit either both of R are methyl or one R is ethyl and the other is hydrogen; 10 T is independently in each occurrence a direct bond or the moiety Ri —j:0CH2— . 15 i ch2ci R1 is independently in each occurrence hydrogen or a Ci-4 alkyl moiety; 20 Z is independently in each occurrence oxygen or 25 X is independently in each occurrence a Ci-6 alkyl moiety; a is independently in each occurrence a positive real 30 number of 1 or greater; b is independently in each occurrence 2 or 3; C-39,462-F 59 o _ -V - C ■■ ■ - >J:J4 " ^ >> O. ✓ 7 -J 244 d is independently in each occurrence a number of from 0 to 2 ; e is independently in each occurrence 0 or 1.

5. Flexibilized advanced epoxy cationic resin comprising the flexibilized advanced epoxy resin according to any one of Claims 1 to 4 which further comprise D. cationic terminal moieties comprising the reaction product of a nucleophile and the glycidyl ether moiet ies. 15

6. Flexibilized advanced epoxy cationic resin compositions according to Claim 5 wherein 20 the nucleophile is a monobasic heteroaromatic nitrogen compound, tetra( cx_6 alkyl) thiourea, a sulfide corresponding to the formula: R6-S-R6 25 an amine corresponding to the formula: R7-fjJ-R8 ; R8 or a phosphine corresponding to the formula: R9-P-R9 ; I >" R9 ,v * v ~ "i *22 DEC J994 ■ C-39,462-F 60 m 61 ^44069 wherein: R"3 is independently in each occurrence Cj _fe alkyl, hydroxy Ci_fa alkyl or two of R& may combine as one 3 to 5 carbon atom alkylene radical thereby forming a 5 heterocycloalkylene moiety; R7 is independently in each occurrence hydrogen, hydroxyalkyl, ^'i-o> alkyl, aralkyl or aryl; jq R3 is independently in each occurrence hydrogen, alkyl, hydroxy ci-6 alkyl, the moiety or two of R8 may combine to form an alkylene radical having from 3 to 5 carbon atoms; 2q R9 independently in each occurrence ci-e alkyl, hydroxy ci-b alkyl or aryl; RlO is independently in each occurrence a c2-10 alkylene group; 2 5 Rll is independently in each occurrence alkyl . 30 electrodeposition comprising an aqueous dispersion of the advanced epoxy cationic resin of Claim 6 in combination with a crosslinking agent selected from a blocked polyisocyanate, an amine aldehyde resin, a phenol aldehyde resin and a polyester resin. 15

7. A coating composition which is suitable for r O #C C-39,462-F 61 >% * 62 ^144 0

8. The use of the advanced epoxy cationic resin of Claim 6 in electrodeposition coating compositions. 10

9. A process for preparing flexibilized epoxy resins comprising A. reacting a polyglycidyl ether of a di- or tri-hydroxy Ci-6 hydrocarbon or water initiated polybutylene glycol with two or more moles of a polyaromatichydroxy compound per mole of polyglycidyl ether of polybutylene glycol under conditions such that substantially all of the glycidyl ether moieties react with aromatichydroxy 15 moieties of the polyaromatichydroxy compounds; B. thereafter reacting the reaction product with an excess of one or more polyglycidyl ethers of polyaromatichydroxy compounds, optionally one or more 20 polyaromatichydroxy compounds and, optionally one or more chain terminators under conditions such that the aromatichydroxy moieties of the reaction product, and optionally the polyaromatichydroxy compound, react with the glycidyl ether moieties of the polyglycidyl ethers of polyaromatichydroxy compounds wherein the terminal moieties of the product are glydicyl ether moieties. 25 v ^ .<L ■ 30

10. A process according to Claim\, rQ, wherein the poiyyiycidyi ether of polybutylene glycol and the polyaromatichydroxy compound are contacted in the presence of a catalyst for the reaction of a hydroxy moiety with a glycidyl ether moiety, the temperature of the mixture is increased until the reaction mixture . \ C-39,462-F 62 * /LLi hj.f 63 begins to exotherm and the reaction mixture is reacted until substantially all of the glycidyl ether moieties react with the aromatichydroxy moieties; thereafter one or more polyglycidyl ethers of an polyaromatichydroxy compound, optionally one or more polyaromatichydroxy 3 compounds, and optionally one or more chain terminators are added, the temperature of the reaction mixture is raised to a temperature at which the reaction mixture exotherms and the mixture is reacted until the desired jq molecular weight is reached. 15 20 25 30 C-39,462-F 63 </div>