CA2114795A1 - Internally flexibilized advanced epoxy resin compositions and coatings therefrom - Google Patents

Abstract

The invention relates to flexibilized advanced epoxy resins comprising the residue of A) one or more polyglycidyl ethers of a water or di- or trihydroxy substituted C1-6 hydrocarbon initiated polybutylene glycol; B) one or more polyaromatichydroxy compounds;
and C) one or more polyglycidyl ethers of polyaromatichydroxy compounds; wherein substantially all of the glycidyl ether moieties 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;
each polyaromatichydroxy compound is bound to at least one polyglycidyl ether of polybutylene glycol or to at least one polyglycidyl ethers of polyaromatichydroxy compounds through the reaction product of an aromatichydroxy moiety with a glycidyl ether moiety;
most of the polyglycidyl ethers of polyaromatichydroxy compound are bound to at least one polyaromatichydroxy compound through the reaction product of glycidyl ether moiety and an aromatichydroxy 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 compounds to polyglycidyl ether of polybutylene glycol is at least about 2.0 to about 1.0; and sufficient polyglycidyl ethers of polyaromatichydroxy compounds are present in the resin such that the terminal moieties of the resin are glycidyl ether moieties from the polyglycidyl ethers of polyaromatichydroxy compounds.

Description

WO g3/04104 ~ PCr/US92/07234 .

INTERNALLY FLEXIBILIZED ADVANCED EPOXY RESIN COMPOSITIONS AND COATINGS i~
TH E REFROM

The invention relates to internally flexibilized advanced epoxy resin compositions ::
5 flexibilized with in~ernal poiybutylene glycol units, and a process for the preparalion o~ such internally flexibilized advanced epoxy resins. The invention further relates to coatings pre~ared from such internally flexibilized advanced epoxy resi ns, such coatlngs are useful in cathodic ~ -electrodepositions, powdercoating applications, marine and maintenance and in ;ood and ;
beverage applications.
' ``~
Advanced epaxy resin compositions are used in a ~/ariety of applications, such as in ~;
coatings compositions in several fields, for example in cathodic electrodeposition, powder coating of pipes and structural elements, in liquid coating compositions for food and beverage cans and marine and maintenance applications. AdYanced epoxy resin based coatmgs have .
15 advantageous properties such as adhesiveness, strength, hardness and chemical resistance Unfortunately, cured advanced epoxy resin compositions suffer from a I ack of flexibility, which can have 3 negative effect on other pro~erties such as protection of substrates from corrosion.

A representative use of advanced epoxy resins compositions which exhibits such 20 proolems is the field of cathodic electrodeposition. Cathodic electrodeposition of a film composed of an amine modified eooxy resin, crosslinker, plgment ana ootionally other reslnous componerlts onto an eiectrically conductive article is an imDortant Industrlal orocess. 't constltutes :he usual manner n which automoblle and truck bodies as well as aDpiiance and other !arge cor~plex rnetallic sur,ace bodies are protec~ed against corroslon. 'n Der;ormlr~g the 25 e!ectroaeooslt on, ~he conclucll~e artlc,e. a~ucle to be coate~. forms on~ electroae anc~ is rnrnersed :n a coatlng Datn ~nade from an aaueous disr~erslon ot tne fii~ formmg amlne modifiea epoxy ~esln and otner comDonerts. ~r elec~rlcal current IS Dasserd be~ween t~e arucle and ~he counterelectrocle In he electrodeposlllc)n oath. A charge on ~he article causes deposl;;or, o~ e res,ns and otner comporents m tne oatn on the article o be coatecl so as to WO 93/04104 ~ 7 9 ~i PCr/US92107 ~34 produce the electrodeposited fiim. The de~oslted film is then baked or otherwise hardened to yield a coating of a substantially uniform thlckness and protective characteristics -~
:' . ' A number of advances in the protective properties of electrodeposit resln 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; 3,962,165; 4,071,428; 4,101,468; ~,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 by extending the molecular length of the aromatic diepoxide starting 10 material with polyols, polyamines, polyether polyols, polyester polyols and other similar types of extension agents. US Patent 3,839,252 describes modification with Dolypropylene glycol. US
Patent 3,947,339 teaches mc dification with polyesterdiols or polytetramethylene glycols. US .
Patent4,419,467describesstillanothermodifi~ationwithdiolsderivedfronncyclicpolyols ;~
reacted with ethylene oxide. In those embodiments wherein polyether polyols and polyester ~ ~-15 polyo~s 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 required to effect the reaction between the primary aicohols and the epoxy ;~ ~`
groups involved. Furthermore, these reactions require long cook times and are subject to ; ~: -gellation because of competitive polymeri~ation of the epoxy groups by the base catalyst. In - ~ ~
20 addition epoxy resins containing low levels of chlorine are required to prevent deactivation of .; -this catalyst.

European Patent Application 300,504A discloses the preparation of flexi bili~ed -. ~ ".
~ . .
epoxide compounds by reacting an aromatic diol with diepoxides which are diglycidyl ethers of `
25 aromatichydroxy compounds, or a bis-(labile hydrogen functionalized) alkoxy arylene . ~ .
compound. European PatentApplication 315,164disciosesa coating resin composition which comprises the reaction produn of a diepoxide compound which is a diglycidyiether of a bisphenol A (bis-(4-hydroxy phenyl)propanel initiated polyalkylene oxlde, a bisphenol, optionally a bisphenol diglycidylether, and an amine, having an actlve hydrogen. It is disclosed 30 therein that the bisphenol A initiated ~olyalkylene oxide diepoxide ~esults In an improved electrodeposition coating. Commoniy assigned ~atent application EP 253,405 discloses an ~:~
ad~Janced epoxy cationic resln prepared by reacting In the presence of a sultable catalyst (A) a composition comprlsing (1) at ieast one diglycldyl etner of a polyoi and (2) at least one diglycidyl ether of a dihydric Dnenol wlth (B~ at least one dinydric nnenol and or tlonally (C) a 35 monoflJnc;ional capping agent. Componen~s ~A) ana (B) are e~nDloyea In such quantities tna~
the resultant epoxy resin has an average epoxide welght from 350 to 10 OOQ

- 2~
:" .:, "`'.
- -i;

WO 93/041 04 ~ I ~i 7 t~ PCI /US92/07234 T-le resins disclosed exhibit some flexibility problems and do not provide superior anticorrosion prope!ties. Additionally, some of the processes disclosed for preparing the resins do not efficiently incorporate the polyalkylene glycol containing diepoxides into the backbone : ~
of the advanced resins. .:
: .
In electrodeposition it is desirable that the resins in the coating have a low viscosity to facilitate processing and control of the coati ng thickness. It is also desi rable that such coatings demonstrate low water permeability as this property is important in the inhibition of corrosion. Additionally it is desirable that such coatings demonstrate good 10 flexibility. The problem isthat asthe 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 elec~rodeposition 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 15 further needed is a process which allows efficient incorporation of the flexi bi i izi ng agent i nto the backbone of the advanced epoxy resin. -:

The invention relates to flexibilized advanced epoxy resins comprising the residue :
of :-A. one or more polyglycidyl ethers of a water or di- or triinydroxy substituted Cl .6 hydrocarbon initiated polybutylene glycol;
B. one or more polyaromatichydroxy co~pounds; and C. one or more polyglycidyl ethers of polyaromatichydroxy compounds;

25 wherein substantially all of the glycidyl ether moieties of the polyglycidyl ethers of polybutylene glycol are bound to the polyaromatichydroxy compounds through the reaction product of the glycidyl ether moieties with the arornatichydroxy moieties;
each polyaromatichydroxy compound is bound to at least one polyglycidyl ether ofpolybutylene glycol or to at least one polyglycidyl ether of a polyaromatichydroxy compound 30 through the reaction product of an aromatichydroxy moiety with a glycidyl ether moiety; most of the polyglycidyl ethers of polyaromatichydroxy com~ounds are bound to at least one polyaromatichydroxy compouna through the reaction i~roauct of glycidyl ether moiety ana an aromatlchydroxy molety; each reslaue of a polygiycidyl ether of polyaromatlcny~roxy cornpound Is bound to at ieast one oolyaromatichydroxy comoound through the reactlon of 2 35 glycldyl ether moiety and an aromatichydroxy molety;

where!n the mole rallo of polyaromatichydroxy compound to oolyglycidyl ether of polybutyîene qlycol is at least 2.0 to 1.0: and sufficient i~oiygiyc dy! ether of -3- :

4 ~ 1 1 4 7 ~ ~ PCr/US92/07234 polyaromatichydroxy compound is present in the resin such tha-t the terminal moieties of the resin are glycidyl ether moietles from the polyglycidyl ethers of polyaromatichydroxy compounbs.

In another aspect the invention is a process for the preparation of such flexibilized advanced epoxy resins cornprising A. reacting a polyglycidyl ether of a di- or tri- hydroxy C1 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 10 the glycidyl ether rnoieties of the polyglycidyl ether of polybutylene glycol react with .
aromatichydroxy moieties of the polyaromatichydroxy compounds;
B. thereafter reacting the reaction prc duct from A with an excess of one or more polyglycidyl ethers of polyaromatichydroxy compounds, optionally one or more polyaromatichydroxy compounds, and optionalIy one or more chain terminators, under :
15 conditions such that the arornatichydroxy moieties rea with the glycidyl ether moieties .
wherein the terminal functional moieties of the product are glycidyl ether moieties.

In anotheraspectthe invention relatesto flexibilized advanced epoxy resins ; .
prepared by the above-desaibed proce~s. In yet another aspect the i nvention is directed to . .
20 advanced epoxy cationic resins having a charge density Qf from 0.2 to 0.6 milliequivalents of ` .
cationic charge per gram of resin, wherein the terminal epoxy moieties of the above-described . ~ :~
res~ns have been reacted with a nucleophile and treated to render the resulting moieti~s ' ::
cationic. ~ . .

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 30 invention demonstrate improved e!ongation and imDact resistance along with exceptionai combination of elongation, impa~t resistance, and corros~on resistance as compared to conventional resins.

A major advantage of the invention 15 the efficient incorporation of an Improved3 flexibilizlng 3gent ,nto tne internal backbone Ot t~.e advancecl eDoxy resins. Thus the backbone of the flexibllized eooxy resln of this ~nventlon contalns at least one unit of the flexibilizing comoonent in its Inlerior. The flexibilizing unlt is the residue of a polyglycidyl ether of a water ~ . .
or di- or ~n hyc~roxy s~Jbstltuted C1-6 nyarocarbon Inltlated polyDutylene glycol, whicn means ' ` ~-;
..

211~'7-g5 WO ~3/04104 PCI/US92/07234 herein that the glycidyl ether moieties of such compound have been reacted wlth aromatichydroxyl groups so as to incorporate such polybutylene glycol into the backbone of the flexibilized advanced epoxy resins. The flexibilizing agent is ~repared by reacting water or `;
a di- or tri- hydroxy substituted C1-6 hydrocarbon with butyiene oxide units, so as to react the 5 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 C1-6 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 10 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 ini~iator. `~

Included among the initiators for the flexibilizing unit are water, ethylene glycol, propylene glycol, butane diols, such as 1,4 butane diol, trimethyol propane, neopentylglycol t S and glycerol. The most preferred initiator is water. Preferably, the 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 glcyol, has a molecular weight of 2000 or less, more preferably 1000 or less, and most preferably 600 or .
less. rhe molecular weights referred to here are number average molecular weights. The 20 flexibilized advanced epoxy resins of this i nvention preferably contain S percent or greater by weight of the residue of the glycidyl ethers of polybutylene glycol in the backbone, and more preferabiy 10 percent or greater. Preferably, the flexibilized advanced epoxy resins of this invention contain 50 percent or less by weight of the residue of polyglycidyl ethers of ~ ~ ~
polybutylene glycol in the backbone, more preferably 30 percent or less by weignt. In a ;
25 preferred embodiment, the glycidyl ethers of polybutylene glycol correspond to formula 1 R R
Z~HCHO~CH2-T-C~CH~) 1 30 wherein R is independently in each occurrence hyarogen, methyl or ethyl with the proviso that for each R R
~HCHO~
J
~5 ~:
unlt either ~oth of R are methyl or one R is ethyl and the other is hydrogen;
T Is inde~oendently in each occurrence a direct ~ond or the molety ' ~
, :, '~;

` ~' ' WO 93fO4104 2 1 1 4 7 ~ ~ PCI/US92/07234 ~
Rl , .~
,,~
-OCH2-- ;
!:H2CI : , S '.
R' is independently in each occurrence hydrogen or a Cl~ alkyl moiety;
Z is independently in each occurrence oxygen or ., \ Jb ; ~``

X is independently in each occurrence a straight or branched chain C1-6 alkyl rnoiety; .
a Is independently in each occurrence a positive real number of 1 or greater;
b is independently in each occurrence 2 or 3.
15 Z Is ,t)referably oxygen. X is ~referably a straight or branched chai n Cl .4 alkyl moiety. Preferabiy, . .
a is a real number of from l to 16; more preferably from l to 8 and most preferably of from 2 to 5. Preferably b is 2.

The ini~iator used in this invention preferably is water or corresponds to Formula 20 2~

X~ ) 2 ~`
b 25 wherein X and b are as described hereinbefore.

The polyglycidyl ethers of polybutylene glycol are reacted with polyaromatichydroxy compounds. Polyaromatichydroxy compounds referred herein to compounds which on average contain more than one hydroxy group and which comprises a 30 hydrocarcon backbone containing aromatic moieties, wherein the hydroxy moieties are bound ~ -~
to aromatic moieties di rectly. Preferably the Dolyaromatichydroxy hydrocarbons have two or more aromatic bound nydroxy grouos. The polyaromat,chydroxy comDounds can oe further su~stltuted on the hydrocar~on backbone by halogen moletles. Among preferreci classes of oolyarornatichydroxy comDounds are the bis~nenols, halogenated bisr henols, hydrogenated 35 oisphenols, and novolac reslns, .e. the reactlon ~oroauct of ohenols anci simDle aldehydes, preferabiy formaldehyde ana hydroxy benzaidehyde. Preferred polyaromatichyaroxy compounds ~seful ,n this Invention correspond to formula 3: , `6- ~ `
'"`-.;'``' ~ `

WO ~3/04104 2 ~ 1 4 ~t~ ~` PCI`/USg2~07234 A~OH)C 3 5 wherei n Ar is an aryl moiety; aryi moiety substituted with an alkyl or halo moiety; a polyaryl moiety wherein the aryl moieties are connected by direct bonds, alkylene, 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 10 phenol;
and c is a positive real number greater than 1.

More preferred polyaromatichydroxy compounds include those corresponding to forrnulas4and 5: . `

(R2)m (R2)m HO~R3 ~OH 4 HO~ R4 ~ R4 ~OH S

(R~)m' P

wherein;
R2 is separately m each occurrence C1-3 alkyl or a halogen;
~3 is seoarately in each occurrence C- o alkylene, Ct-10 haioalkylene, C~. o cycloalkylene, 35 carbonyl, sulfonyl, sulfinyl, oxygen, sulfur, a dlrect ~ona or a molety corresponding tO tne formula WO 93/04104 ~ PCr/VS92/07234 (R2)",~H

R4 is inclependently in each occurrence Cl-1o alkylene or Cs so cycloalkylene;
Q is independently in each occurrence a C1-lO hydrocarbyl moiety;
Q' is independently in each occurrence hydrogen, cyano, or a Cl la alkyl group;
m is independently in each occurrence an integer of O to 4;
m' is independently in each occurrence an integer of from O to 3; ; -~
p is a posi~ive real number of O tO 1 0.

R3 is preferably C1-3 alkylene, C1-3 haloalkylene, carbonyi, sulfur, or a direct bond.
R3 is more preferabiy a direct bond, Cl 3 alkylene, or fluorinated propylene ( = C(CF3)2-). R3 is -most preferably propylene. R2 is preferably rrtethyl, bromo or chloro; and most preferably methyl or bromo. R~ is preferably C1.3 alkylene or polycyclic moiety corresponding to the ~ ;
foimula .-~

'25 ~ ~:

30 wherein t is an average number from l to 6 inclusive, preferably l tc3 3, most preferably l . ~ -~
Preferably, m and m' are independently an integer of O to 2. Preferably, p is a oosltive real nurn~er of O to 8; and more preferably ~ to 4. p reoresents an average number, as the cornoounds to which it refers are generally found as a mixture of compouncts with a aistrli~utlon of the units to which p refers. Cycloalkyiene as used herein refers to monocyctic 35 and poiycyclic hydrocarbon moieties. ; `

The most preferred class of polyaromatichdroxy compounds are the dihyaroxy phenois. Preferable dihydroxy phenols include those wh~cn contaln substltuents that are non- ~ ~
-8- ~ :

~''~`.

WO 93/04104 - ~ 1 1 47 ~ ~ PCI/US92/07234 reactive with the phenolic groups. Illustrative of such ohenols are 2,2-bis(3,5-dibrorno-4-hydroxyphenyt) propane; 2 ,2-bis(3,5-di bromo- 2 ,4'-hyd roxyphenyl) propane; 2 ,2-bl s(4-hydroxyphenyl) propane; 2,2-bis~2,4'-hydroxyphenyl) propane; 2,2-bis(3,5-dichloro-4-hydroxyphenyl) propane; 2,2-bis(3,5-dichloro-2,4'-hydroxyphenyl) propane; bis (4-hydroxyphenyl) methane; bis (2,4'-hydroxyphenyl) methane; 1,1-bis(4-hydroxyphenyl)-1-phenyl ethane; 1,1 -bis(2,4'-hydroxyphenyl)-1 -phenyl ethane; 1,1-bis(2,6-dibromo-3,5-dimethyl-4 hydroxy phenyl) propane; bis (4-hydroxyphenyl) sulfone; bis (2,4'-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) sulfide; bis (2,4'-hydroxyphenyl) sul fide; resorci nol;
hydroquinone; and the like. The preferred dihydroxy phenolic compounds are 2,2-bis(4-10 hydroxyphenyl) propane, 2,2-bis(2,4'-hydroxyphenyl) propane (a mixture of the two is commonly referred to as bisphenol A).

As used herein haloalkyl refers to a compound with a carbon cham and one or more of the hydrogens replaced with a halogen, and includes compounds where all of the 15 hydrogen atoms have been replaced by halo~en atoms. Alkylene as used herein refers to a divalent alkyl moiety. ` `

The term hydrocarbyl means any aliphatic, cycloaliphatic, arornatic, aryl substituted aliphatic or cycloaliphatic, or aliphatic or cycloaliphatic substituted aromatic 20 groups. The aliphatic groups can be saturated or unsaturated. Likewise, the term hydrocarbyloxy means a hydrocarbyl group having an 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, carbcxyl, sufonyl, sulfinyl, oxygen or sulfur 25 moieties. `
.
The term residue as used herein refers to the portion of a starting mateffal remaining in the final product after completion of the reaction. The term residue of a polyaromatichydroxy compound means herein that a polyaromatichydroxy comDound has 30 been incorporated into the backbone of the flexibilized advanced epoxy resin wherein the aromatlcnydroxy moleties have reacted with glycidyl ether moleties of the glycidyl ether of polybutylene glycol, or the glycidyl ether moieties of a glycidyl ether of an aromatlcnyàroxy comDound. In a preferred embodiment, the polyaromatichydroxy compounds are nommally dihyaroxy aromatlc comDounds meaning that tne dihydroxy comDouncis are a mlx~ure of 35 compounds resuitlng from the prepara~ion ~rocess, and on average Ihe compounas present have near two nydroxy moietles per molecule.

"",, .

9 ~
", '` ".

WO93/04104 21 1~7~ PCI/US92/07234 ~ ~
The residue of polyglycidyl ethers of poiyaromatic hydrocarbon means,here~r~ ~ -that at least one of the glycidyl ether moleties has reacted with an aromatichydroxy moiety, ~ ;.
wherein the polyaromatichydroxy compound may be further reacted with a polyglycidyl ether ~;
of a polybutylene glycol. The resins of this invention preferably have terminal giycidyl ether S moieties which are derived from the glycidyl ethers of polyaroma~ichydroxy 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. -General Iy these materials are not removed prior to utilization.
....
Polyglycidyl ether of a polyaromatichydroxy compound rneans a hydrocarbon . .~
compound containing one or more aromatic moieties, wherein more than one epoxy (1,2 ~ ~:
glycidyl ether) moiety is bound to the aromatic 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 polyaromaticnydroxy cornpound as used 1 S herein includes partially advanced epoxy resins i.e. the reaction OT a polyglycidyl ether of a . .
polyaromatichydroxycompound and one or more polyaromatichyaroxy com~ounds, whereln : . `.
the reaction product has an average of more than one unreacted e~oxide unit per rniolecule.
, ~
Polyglycidyl ethers of a polyaromatichydroxy compounds (polyepoxides) are - :-20 prepared by reacting an epihalohydrin with a polyarornatichydroxy compound. The preparation of such compounds is well known in the art. See Kirk-Othmer Encyclopaedia of . :
Chemical Techno!ogy 3rd Ed. Vol.9 pp 267-289, "The Handbook of Epoxy Resins" by H. Lee and ~;:
K. Neville (1967) McGraw Hill, New York, and 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:

R ~

CH2 ~H2Y 6 O . '; ~

wherel n 35 Y is a halogen, preferabiy chloro or bromo, and most oreferably cnloro; ;;
and R; is as previously defined.
- -.,~:

- t 0~
:

, .,:

WO 93/04104 ~ 7 ~ ~ PCl`/US92~07234 The polyglycidyl ethers of polyaromatichydroxy compounds useful in the invention preferably correspond to formula 7 ;

R
A~(O-CH2(~H~)C 7 wherein Ar, R and c are previously defined. Rl is preferably hydrogen or methyl. Preferably, c is :
10 5 or less, more preferably from 1 to 3.

The polylycidyl ethers of polyaromatichydroxy compounds more preferably correspond to one of formulas 8 or 9: ~

R' (R2)m (R2)m R1 (R2)rrl (R2)m R ~-CH2CcH20~ R ~CH2CllCH2~ R3~CHzC\tH2 8 ~`~

R~ :

CH2CCH2~RO4/~ R4 ~~H2~ icH 2 ~ ~

(R2~m (R2)~

'~'s`
. 1 ~ i . .

, ~

WO 93/04104 2 1 1 ~ 7 ~ ~ PCI`/USg2/07234 wherein ~1, R2, R3, R4, m, and m~ are as defined previously; r is a positive real number of 0 to 40;
and s is a positive real number o~ 0 to 10. Preferably, r is a positive real nùmber of 0 to 10, and most preferably 1 to 5. Preferably, s is a positive real number of 0 to 8; and most preferably 1 to 4. All 5 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 dihydroxy phenols, bisphenols, halogenated bisphenols, alkylated bisphenols, I
10 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, hydroqulnone, isphenol, bisphenol A, bis,ohenol AP ( 1,1-bis(4-hydroxylphenyl)-1-phenyl ethane), bisphenol F, ~ :
bisphenol K, tetrabromobisphenoi A, phenol-formaldehyde novolac resins, alkyl substituted ~ ~ -phenol-formaldehyde resins, phenol-hydroxybenzaldehyde resins, cresol- ~;
hydroxybenzaldehyde resins, dicyclopentadiene-phenol resins, dicyclopentadiene-substituted phenol resins tetramethylbiphenol, tetramethyl-tetrabrornobiphenol, A
20 tetramethyltribromobiphenol,tetrachlorobisphenolA, tetrabromobisphenolA,any combination thereof and the like. Preferably the polyglycidyl ether of the poiyaromatichydroxy cornpounds is a riominally diglycidyl ether of a polyaromatichydroxy compound, meaning t'nat the aetual materials used are a mixture of compounds resulting from the process for preparation wherein the average number of glycidylether rnoieties per molecule approaches 25 two.

Optionally the advanced flexibilized epoxy resins of this invention can contain the residue of a chain terminator. In practice a chain terminator is a rnaterial which has only one reactive moiety containing an active hydrogen atom. Such chain terminator functions to 30 reduce the molecular weight of the proposed material and are well known i n the art. An example of a preferable chain terminator is paratertiarybutyl phenol.

In the preferred embodiment ~herein the polyaromatichydroxy compound is a nommally diaromatichydroxy compo~Jnd, and tne r olyglycidyl ether o; a polyaromatichy~roxy 35 compound is nomlnally a aiglycidyl ether of a a aromatlchydroxy compound, the advancecl flexlbilized resins of this ~nvention correspond to formula 10:
:

'~

W~9~/04104 ~ 7~, PCI/llS9'2/07234 (~H2TCHCH~-OArO-CH21HTCH2-OAro-E) B ~ H2T~HCH2-OAr ~ CH2CHTCH2-B-CH2TFHCH2-OAr ~ CH2fHTCH2-OArO-E~
\ OH OH OH OH

10 wherein B is independently in each occurrence Z~LH~HC~;

E is independently in each occurrence a moiety according to one of the formulas ~H2TCHCH2 or O

-Ar-CH2 1 HTcH-8t;cH2TfHcH2 OArO-CH2 FHTCH2-OArO-~) OH OH OH

d is independentiy in each occurrence a number of from 0 to 2; ~:
25 e is independently in each occurrence 0 or 1; and Ar, R, T, Z, X, a, b and c are as defined hereinbefore In one preferred embodiment of the invention, the flexibilized advanced epoxy resin are converted to flexibilized advanced epoxy ~ationi~ resins which have a charge density 30 of from 0.2 to 0.6 milliequivalents of cationic charge per gram of resin. Such resins are ~repared by reacting the terminal glycidyl ether moietieswith a nucleophile and thereafter convert~ng the reaction product to ca~ionlc s~ecies. Nucleophiles useful for ,~erformlng ~his reactlon are ~ell-known to t~lose skilled in the art. Dreferred nucleoQhiles are rnonobaslc neteroaromatic nitrogen comDounds, tetra(lower alkyl) thioureas, sulficdes corres~ondincl to formula 11:
3' R6-S R6 - 11 amlnes corresponding to formula 12~

: ,:

WO 93/04104 2 1 1 ~ 7 ~ P~ US92/07234 R7-~ R8 12 ~ ~ `
R8 ' ~. .
or phosphi nes correspondi ng to form ul a 13 :
R9-~-R9 13 R9 ";
wherein;
R6 is i ndependently i n each occurrence lower alkyl, hydroxy lower alkyl or two of R6 may 10 combine as one 3 to 5 carbon atom alkylene radical thereby forming a heterocycloalkylene `
moiety;
R7 is indeper.dently in each occurrence hydrogen, hydroxyalkyl, lower alkyl, aralkyl or aryl;
R8 is inaependently i n each occurrence hydrogen, lower alkyl, hydroxy lower alkyl, the moiety .
R 1 1 - ~
< R l l ; ` :
or two of R8 m,ay cornbine to form an alkylene radical having from 3 to 5 carbon atoms;
R9 independently in each occurrence lower alkyl, hydroxy lower alkyl or aryl;
20 R10 is independently in each occurrence a C2-lO alkylene ~roup;
R1 1 ,s independently in each occurrence lower alkyl.

Preferably the nucleophile is an amine, more preferably a primary or secondary ~ ~
amine. ; ~ `

Representative nucleophilic compounds are pyridine, nicotinamide, quinoline, iso,riuinoline, tetramethyl thiourea, tetraethyl thiourea, hydroxyethylmethyl sulfide, hydroxyethylethyl sulfide, dimethyl sulfide, diethyl sulfide, di-n-propyl sulfide, methyl-n-,oropyl sulfide, methylbutyl sulfide, dibutyl sulfide, dihydroxyethyl sulfide, bis-hydraxybutyl sulfide, 30 trirnethylene sulfide, thiacyclohexane, tetrahydrothiophene, dimethyl amine, diethyl amine, dibutyl amine, 2-(methylamino)ethanol, diethanolamine, N-methylolperidine, N-ethylpyrroliaone, N-hydroxyethylpyrrolidine, trimethylphosphine, trlethyl-ohosphine, trl-n-butyl-Dhosphine, trimethylamlne, triethylamme, tn-n-Dropylamine, tn-lsobutyldmine, hydroxyethyl-dimethylamine, ~utyldimethyiamine, trihyaroxyethylamlne, 35 trl~nenylphospnorus, and N,N.I\-dimetnyipnenethylamlne: anr the ketlmlne derlvatives o~
polyamlnes containlng secondary and c~nmary am~lno groups such as those ~roduced by the reactlon of diethylene triamine or N-arr inoetnylpipera~me with acetone, methyi ethyl ketone or methylisoDutyl ketone. ~ -~

-la WO 93~04104 ~ PCI /US92/07234 In a preferred embodiment the nucleophile is a pnmary or secondary amlne, the polyaromatichydroxy compound is a diaromatichydroxy compound, and the polyglycidyl ether of a polyaromatichydroxy compound is a diglycidyl ether of a diaromatichydroxy compound, 5 and sùch compounds preferably correspond to the following formula 14 ~H,TCHC112~0ArO-C112~;1TCH-OArO-Ci) B tCH2TfHCH2-OArO~CH2FHTCH2-B-CH2T I HCH2-OAr~ CH2CHTCH2-OArO~
~ OH OH OH Oh wherein~
G is independently in each occurrence a moiety according to one of the formulas:
~H2TCHCH2 N -(R7)(RB)2 --CH2TCHCH2-O-H -OH A- ; (R7)(R8)2 N~A or ~ ~:
-... ...
OArO-CH2 l HTCH-BtCH~TfHCH2 0ArO-CH2 j~HTCH2-OArO~
OH OH Ql I
A- is the anion of an acid as described here;nafter; . :
and Ar, B, R, R7, R8, T, Z, X, a, b, c, d and e are as des~ribed hereinbetore.

The flexibilized advanced epoxy resins of this invention preferably exhibit a weight average molecular weight of 900 or greater, more preferably 1200 or greatef, and most preferably 1500 or greater. The flexibilized advanced epoxy resins of this invention preferably have a molecular weight of 50,000 or less, more ~referably 30,000 or less, and most preferably 20,000 or less. The flexibili~ed advanced epoxy resins of this inventlon preferabiy have an eDoxy : ~:
equivalent weight (EEW~ of 450 or greater, more preferably 600 or greater, and most ~ .
preferably 800 or greater. The flexlbilized advanced epoxy reslns of this inventlon preferabiy ave an EEW of 5,000 or less, more preferably 4,000 or !ess, and most prerera~ly 3,000 or less.

The Inventors na\/e recognized tnal tne reacti~Jity of a ~olyglycldyl ether of a .
polybutylene glycol with a polyaromatlchydroxy com~ound Is much iower Ihan the reactlvlty of a polyglycidyl ether or a polyarornatichyaroxy comr~ound wlth a oolyaromatlchyclroxy compound. Theretore, unless the process conaitlons are carefully chosen, It Is difficult to '~'' WO93/04104 21 ~ PCr/US92/07234 .

efficiently Incorporate the poiyglycidyl of a polybutylene glycol in~o the internal structure of and advanced epoxy resin. ~he process of this invention involves first reacting the giycidyl ether ~-of a water or di- or tri hydroxy substltuted C1.6 hydrocarbon initiated polybutylene glycol with the polyaromatichydroxy compound under conditions such that substantially all of the glycidyl ;
5 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 polyglycldyl ether of a polyaromatichydroxy compound under conditions such that the terminal ' -~
aromatichydroxy moieties of the reaction ~roduct react with the glycidyl ether moieties of the polyglycidyl ether of the polyaromatichydroxy compound, such that the terminal groups of the ;
10 flexibilized epoxy resin are primarily glycidyl ether moieties. OptionalIy, 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. ~ `
. .
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 hydrocari30ns and alkanols, glycol ethers and ketones. It is advantageousto include epoxy resin advancement catalyst, such as compounds containing 20 amine, phosphine, heterocyclic nitrogen, ammonium, phosphonium, arsonium, or sulfonium mo~eties. Preferred catalysts are the ,ohosphonium compounds. In the embodiment where the catalyst is a phosphonium or an amine preferably 500 ppm (parts per million~ or more of the catalyst ~s present, more preferably 700 ppm or more. Preferably such catalyst is present in amounts of 3,000 Dpm or less, more preferably 2000 ppm or less. Thereafter the reaction mixture is heated until an exotherm begins, generally at from 140 to 1 50C. Preferably, the `~
temperature of the mixture is increased at a rate of from 1 to 2C 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 30 by cooling. The reaction time is dependent upon the concentration of catalyst, materials present, presence of solvent and the reactivity of materiais. Preferably reaction times are 15 mlnutes or greater, more preferably 3û minutes or greater. Preferably reaction times are 4 hours or iess, and more preferably 3 hours or less In a Dreferred embodiment, the amount of oolyaromatichydroxy compound contacted with the ootyglycidyl ether of the polybutylene 35 glycol Is s~,fficient to react wltt~ all of the glycidyl ether molet~es of the potyglycidyl ether of Dolybutylene glycol. Preferabiy two moles of ~olyaromatlchyaroxy material or greater is oresent per mole of polyglycidyl etner of polybutylene glycol. In some embodiments It may be aavantageous to nave a slgnificant excess of poiyaromallchydroxy material where s;-ch WO 93/04104 2 1 ~ ~ 7 ~ PCI/US92/07234 material would be advantageous in further advancmg the reaction product in the second ste~.
Once the reaction is complete, the reaction product may be recovered from the reaction mixture, or alternatively and preferably the ~olyglycidyl ether of the polyaromatichydroxy compound is thereafter added to the reaction mi xture and the second step of the reacti on i s 5 performed.

In the preferred embodiment where a diaromatichydroxy compound is reacterJ ~
with the polyglycidyl ether of the polybutylene glycol based material the reaction product of thefirststeppreferablycorrespcndstoFormula 15~

Z~H~Ho3~cH2-T-~H~-oAroH ) 15 wherein Z, T, R, R1, Ar, a, and b are as hereinbefore defined.

In the second step of the reaction, the reaction product of the first step is ~ . ;
contacted with a polyglicyidyl ether of a polyaromatichydroxy compound, and additional polyaromatichydroxy compound andlor chain termi nator. Preferably, the molar amount of .
polyglycidylether of a polyaromatichydroxy compound is present in a ratio of greater tt1an 1.0 ~ `
20 as compared to the moles of the above-mentioned reaction prodiuct of the first stej2 and more pre~rably 1.5 moles or greater. Thereafter, the mixture is heated until exotherm occurs. `
Optionally, catalyst for the advancement of eooKy resins may be present. Alternatively, a : `.~
sufficient amount of 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 25 presence of a solvent. Solventswhich may be used are those which are typically used as solvents ~ -for epoxy advancement reactions. A reaction in solvent may be advantageous wherein heat : 5 control is desired. The advancement reaction is preferably performed at a temperature of 1 30C
orabove,asbelow 130Cthereactiontimeistooslow. Preferablythereactionisperformedata temperature o~ 230C or less, the poiymer reacts to fast above such temperature and unwanted 30 colors rnay be formed due to the Dresence of oxidated byproducts. More preferably the reaction tem~erature is 1 80C or below. The temperature wnich may be used for the reaction .
depends on whether or not a solvent Is used, and its nature. The reaction mixture is preferably neated at a rate such that the temperature increases trom 1 to 2C per minute until exotherrn is achieved. Thereafter eievated ~emDeratures are maintained until the desired molecular weight 35 and epoxy eauivalent v~elghts are reached. The Dolyeooxlde acivancement reaction Is ailowed ;
to ~roceed for a ~Ime sufficient to result in substantlaily comDiete reaction, preferably 15 minutes or greater, !nore Dreferai~ly 30 mlnutes or greater. Preferabiy the maximum reaction time is 1~ hours or less and more ~referabiy 2 hours omess. The flexibili~ed advanced epoxy -~ 7-. :

WO 93/04lO4 ~ 1 1 4 7 (~ ~ PCl`/US92/07234 : i-resinsof this invention can thereafter be recovered and formulated for use in vario~s coatings ;;
applications~ The flexibili~ed 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 coati ngs useful in industriat 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 10 a form useful for such coatings.
~:-In one preferred embodiment, the flexibilized advanced epoxy resins of this ~' invention are converted to cationic resi ns ;.or use i n cathodic electrodeposition coatings by reacting at least some of the glycidylether moieties of the resin with a nucteophilic compound 15 and adding an organic acid and water at some point during the pre~oaration. It is also ~oossible to react at least some of the glycidyl ether moieties with a nucleophile salt formed by ; -prereacting the nucleophile with the organic acid. .~

~ . .. ..
Substantially any organic acid, especially a carboxylic acid, can be used in the20 conversion reaction toform onium salts so long as the acid is sufficiently strong to p-omote the reaction between the nucleophilic 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 produc, the acid should be sufficiently strong to protonate the resultant tertiary amine pro~uct to the extent desired. Monobasic acids are normally preferred ~H ~ A-). Preferable 25 organic acids include, for example, alkanoic acids having from 1 to 4 carbon atoms (e.g., acetic acid, propionic acid, etc.), alkenoic acids ha~in~ 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 and acetic acid being most 30 ,oreferred. The anion can be exchanged, Qr course, by conventional anion exchange techniques.
See, for example, US Patent 3,959,106 at column 19. Preferable anions are chloride, bromide, bJsulfate, bicaroonate. nitrate, dinyclrogen ohosQhate, lactate and alkanoates of 1-4 carbon atoms. Aceta~e and lac~ate are the most preferred anions.

The con~ers~on reaction to form cationic resms Is normally conducted by blenaingtherea.antstogether. ~:iooaresultscanbeacnievedbyuslngsubstantlallystoichiometnc amounts of reactants although a slight excess or deficiency of the epoxy- containi ng resi n or .he nucleoDhil~ic compounds can Qe usec. ~ tn weak ac!ds, useful ratlos of tne reactants range 1 8~

WO13/114104 211~7~ PCI/US9Z/07Z34 :~

from 0.5 tO 1.0 equivalent of nucleoohilic compounds per glycidyl ether moiety of the resin and for organlc acids from 0.5 to 1.1 equlvalents of organic acid per glycidyl ether moiety. These ratios, when combi ned with the preferred epoxide content resins described above, provide the ; ~`
desired range of cationic charge density required to produce a stable dispersion of the coatlng composition in water. With still weaker acids a slight excess of acid is preferred to maximi2e the :
yield of onium saits. 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 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 amo~Jnts of from 5 to 30 moles per epoxy ... ..
equivaient. It is advantageous to include minor amounts of organic solvents i n the reac~ion `, mixture, ~he presence of which facilitates contact of the reactants and promotes the reactlon ;
15 rate. One preferred class solvents are the monoalkyl ethers of the C2-4 alkylene glycols, ~vhich ; ~
includesthe monomethyl ether of ethylene glycol, the monobutyl ether of ethylene glycol, etc. . ~ ~.
When the dffired degree of reaion is reached, any excess nucleophilic compound can be removed by standard methods, e.g., dia!ysis, vacuum strip,oing and steam distillation.
~"'`'.''.'~"`
The cationic, advanced epoxy resins of this invention in the form of aqueous dis~e~ rsionsare useful as coating compositions, especially when applied by electrodeposition. , The coating compositions containing the cationic resins of this invention as the sole resinous component could be used but it is preferred to include crosslinking agents in the coating ~ r;
composition, so that the coated films, when cured at elevated temperatures, will be crosslinked 25 and exhibit improved fllm Droperties Materials suitable for use as crossl inking agents are those .
known to react with hydroxyl groups or amino protons; and include blocked polyisocyanates;
amine-aldehyde resins such as melamine-formaldehyde, urea-formaldehyde, ben~ogucinine-formaledyde, and their alkylated analogs; polyester resins, and phenol-aldehyde resins.
Preferred crosslinki ng agents are the blocked polyiso~yanates which, at elevated temperatures, ;~
30 deblock and form isocyanate groups which react with the hydroxyl grouDs of the resin to crossiink the coating. Such crosslinkers are Drepared by reaction of the polyisocyanate with a monofunctlsnal active-hydrogen compound. ExamDles of polyisocyanates and isocyanate~
functional preDolymers der~ved from ~olylsocyanates and oolyols using excess isocyanate grou~s suitable for preparalion of t~le crossii nking agent are ~escrl bed i n U5 Palent 3 ,959,106 35 toBosso,etal.,InColumn15.Iines1-57.

The blocked Dolyisocyanate cross!inking agents are incorporated Into the coating ~ ~
composition at levels corresponding tO from 0.2 to 2.0 blocked isocyanate groups per hyaroxyl -~ ~ .
~ 9 ~ ~
.

.

WO 93/04104 2 1 ~ 4 7 ~ ~ P(~r/US92/07234 group of the cationic resin. The ~referred level is from 0.5 to 1.0 blocked isocyanatè group per resin hydroxyl group. A catalyst optionally may be inciuded in the coating com,oosition 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 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 i n 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 optionalIy any additives such as ~ ~ -10 catalysts, solvents, surfaants, 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 frorn 10 to 25 percent by weight for application by electrodeposition. ~:

Pigmented coating compositions are prepared by 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 i n the art. ~igments and extenders known in the art are useful in thffe coatings, and include pigments which increase the corrosion resistance of the 20 coatings. E~xarnples of useful pigrments or extenders include titanium dioxide, talc, clay, lead o~ude, lead silicates, lead chromates, carbon black, strontium chromate, and barium sulfate.

The pH andlor conductivity of the coating compositions may be adjusted to ~
desired levels by the addition of compatible acids, bases, and/or electrolytes known iri the art. ~;
25 Other add;ti~ves such as solvents, surfactants, defoamers, anti-oxidants, bactericides, etc. may also be added to miodify or optimize properties of the compositions or the coating in accordance with practices known to those skilled in the art.

The coating compositions of the invention may be applied by cathodic : ~:
30 electrodeposition, wherein the article to be coated is immersed in the coating composition as the cathode, with a sultable anode in contact with the coating composition. When sufficlent vloltage 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 l ,000 volts, more ~referably from 50 to 500 volts. The film thickness achieved increases wlth increasing voltage. Thicker films are achieveà
35 by incorporatlon of the diglycidyl ether of DolyDutyiene glycol into the r ackbone of ~he :, catlonic res~ns of the invemion. Control over the final thickness may be excerclsed by aclj usting the amount of that component used. The voitage is applied for between a few seconds to several minutes, preferably frorn ~wo rinu~es over which time the current usuaily aecreases as . ~
~ . 20- : `

. .
- ~

WC~ 93~04104 2 1 1 ~ 7 ~ 5 PCI/US92/07234 a resistive film is deposlted. Any electrically conductive substrate may be coated in this fashion, especially metals such as steel and aluminium. Otner aspects of the electrodeposition process are 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 iscuredbyheatingatelevatedtemperatures,preferablyrangingfrom 100to200C,for periods of preferably from 1 to 60 minutes.

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 10 conditions such that continuous films are formed, without conversion to cationic species.
Processesforpreparingsuchpowdercoatingsaregenerallywell knowntothoseskilled inthe art.

In another embodi ment the flexibi lized advanced epoxy resi ns of this i nventi on 15 can be used in solvent coatings. In such an embodimentthe flexibilized advanced epoxy resins -and a curing agent can be dissolved in a solvent and such mixture can be coated onto a substrate and exposed to curing conditions. Preferred solvents are alkyl substituted ben2enes, ~ .
ketones, lower alkanols, glycol ethers, chlorinated alkanes, and dimethyl formamide. The preferred solids level is from 25 to 80 % by weight; and preferably from 30 to 60 % by weight.
20 Generally curing conditions cornprise exposing the coated substituted to temperatures from 20 to ~50C under conditions such that the solvents can be removed from the coating.

The ~lexibilized advanced epoxy resins of this invention are cured with known curing agents for epoxy resins. In preparing coatin~s the flexiblized epoxy resin compositions 25 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 artisan to react with polyepoxides or adYanced epoxy resi ns to form hardened fi nal products and which function to cure the epoxy resi n.
The polyhydroxy comDounds described herei nbefore wherei n the hydroxy rnoieties are bound to aromatic moleties are among suitable curmg agents. The novolac r~ased compounds and the bisphenolic ComF)ounds are the ~referred polyhydroxy com~ounds ;or use as curing agents. Examples of other Dreferable curing agents :nclu~e the r~olybasic acicis and 35 their anhydrides; other types of aclds containing sul fur, nitrogen, unospnorus or naiogens;
soluble adducts of amlnes and polyepoxides and thei r salts, SUCh as descri bed i n US 2 65 t, 589 and US 2,640,037; acetone soluble reaction products of polyamines and monoepoxides: ~he acetone soluble reacti on prod UCIS O; poiyami nes wlth unsatu rated ?ilri I es;; m Idazol ne 2t~

W O 93~04104 ~ 1 1 4 7 ~ ~ - PC~r/US92/07234 com~ounds obtained by reacting monocarboyxlic acias with polyamines; sulfur and/or phosphorus-containing polyamlnes 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 5 acrylate; and many other types of reaction products of the amines; boron trifluoride and complexes of boron trifl uoride with amines, ethers, phenols and the like; Friedel-Crafts metal salts, such as aluminum chloride, ~inc chloride, and other salts, such as zinc fluorborate, magnesium perchlorate and ~inc fluosilicate; inorganic acids such as phosphoric acid and partial esters thereof including n-butyl orthothiophosphate, diethyl orthophosphate and 10 hexaethyltetraphosphate; polyamides containing active amino and/or carboxyl groups, and preferably those containing a plurality of amino hydrogen atoms, especially preferred ~ ;
polyamidesarethosederivedfromthealiphaticpolyamidescontainingnomorethan 12 carbon atoms and ~olymeric fatty acids obtained by dimerizing and/or trimerizing ethylenically unsaturated fatty acids containing up tO 25 carbon atoms; and melamlne reaction products 15 containing methylol substituents.
' ~
Preferred classes of curing agents are the polyamines and amides. Such Dreferred ` .
curing agents include aliphatic polyamines, polyglycoldiamines, polyoxypropylene diamines, poiyoxypropylenetriamines, amidoamines, imida~olines, reactive polyamides, ketimines, 2 a araliphatic polyamines (i.e. xylylenediamine), cycloalipihatic amines ~i.e. isphoronediamine or diaminocyclohexane) menthane diamine, 3,3-dimethyl-4,4-diamin~dicyclohexylmethane, heterocyclic amines ~aminoethyl piperazine), aromatic polyamines, (methylene dianiline), ~.
d~aminodiphenyl sulfone, mannich base, phenalkamine, N,N'N"-tris(~amlnohexyl) melamine, -.
and the like. Most preferred are cyanamide, dkyandiamide, and its derivatives, 25 diaminodiiphenyl sulphone and methylene dianiline.

The flexibili~ed advanced epoxy resin tompositions of this in~ention 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: l to 2: 1; more Dreferably from 30 0 6: l .4 to 1.4: 0.6; even more preferably from 0.8: 1.2 to 1.2: 0.8 and most ~referably from 0.9: l.ltol.l :O.g.

The coatings of this invention aemonstrate excellent adheslon, resistance to cathodic disDondment. excellent flexibility and imDact reslstance, goo~ comDatibiiity wlth a 35 widevarietyofreslnous~inders,suchasacryiics,alkyds,polyestersaswellascurlngagentslike polyamines, melamine or Dnenol resins.

:
`:"
.

WO 93/04104 2 1 1 ~ 7 ~ ~ PCr/US92/07234 The following examDles are included for illustratlve purposes only and do not limit the scope of the claims, Unless otherwlse stated all parts and percentages are by weigh~, ....

EXAMPLE l - Reaction of polypropylene glycol diglycidyl ether, bisDhenol A and diglycidyl ether -':
of bisphenol A. :,~,. .
Not an example of the invention. : -To a to a 51 glass reactor are charged 1550.4 g of a diglycidyl ether of bisphenol A
having an EEW of 1$7.0 (8.33 epoxy eq), 618.0 g of a diglycidyl ether of polypropylene glycol ~ -(EEW of 334.0) prepared from a 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 100C and 2.9 g of alkyltriphenyi phosphonium càtalyst is added. The reactor is slowly ~ -' heatedtol40C.At 140Cthereactionmixtureexothermsandthetemperaturerisestol60C. .
Thetemperatureismaintainedatl60Cfor60minutesatwhichtlmeasampleofthereaction '~
15 mixture is taken which demonsuates 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. ,' '.', ' '`
~ .

~ .

,~

-23- .

WO 93/04104 2 1 1'~ 7 9 ~ Pcr/uss2/o723~ ~

The solid resin is converted into a water-dispersed form usable for the formulation of cathodic electrodeposition primers ~y following procedure. In a reactor 620 g of 5 the solid resin is dissolved in a mixture of 34.4 g xylene and 34.4 g Dowanol~ PPh glycol ether, the phenyl ether of propyiene glycol at a temperature of 11 0C 467.4 g of a 70 wt % solution of blocked polymeric methylene diisocyanate crosslinker in methyl isobutyl ketone is ~lended with the resin solution. Then 40.7 9 of a 73 wt % solution in methylisobutylketone of the diketimine of methyl isobutylketone and diethylenetriamine is added, followed by 3~.1 g of 10 methylethanolamine. The reactor is cooled to keep the reaction temperature from rising over 110C.Atemperatureof 110Cismaintainedfor60minutes.Then38.3gof Dowanol~ PPh glycol ether is added to the reactor. A second reactor is now prepared containing a mixture of a 1306 9 of deionized water, 39.3 9 of lactic acid (0.31 eq. of acid) as well as 17.2 9 of a mixture of suitable cationic surfactant and defoamer. Under strong stirring the hot resin mixture is slowly 15 poured into the second reactor, whereby a low viscosity dispersion is obtai ned. The dispersion is diluted further by the addition of 637.0 9 of deionized water. The dispersion is heated to 65C, 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 1 50C, is determined to be 36.40 % . The dispersion is mixed with a commercially available .
20 pigment paste and diluted by addition of deionized water so that the final Pigmented dispersion has a O.3: 1 ratio of pigment to binder at a solids content of 20 wt % . ~ ;
'::
EXAMPLE 2 - Reaction of diglycidyl ether of polypropylene glycol with bisphenol A and subs~quent reaction of the product with diglycidyl ether of bisphenol A
25 Not an Example of the Invention.

To a reanor similar tO the one described in Example 1 is charged 618.1 g of the diglycidyl ether of polypropylene glycol described in xample 1 and 831.6 9 of bisphenol A
(7.24 eq of phenolic hydroxyl). The mixture is heated to 1û0C and 2.9 g of 30 al kyltri~henyl phosphonium catalyst is added . The reactor is slowly heated to 1 50DC ( 1 to 2C Der mlnute). At 1 50C an exotherm begins and the reaction temperature increases to 1 60C The temoerature is maintained at 160C untiI the welght percentageof eDoxy in the mlxture Is ess than 0.1 Darts by weight: about 60 minutes~ To the reaction mixture is added 1550 4 g of the diglycidyl ether of bisphenol A descrlbed in ExamDle 1 (8.33 eooxy equivalents). The ~ Trademark of The Dow Chemical Company WO 93/04104 2 1 1 4 7 ~ ~ PCI/US92/07234 temperature drops to 1 10C as a result of this addition. The mixture is mixed for 5 minutes and then the temperature is slowly raised by heating ( 1 to 2C per minute). At 140C an exotherm begins and the temperature rises to 1 70C. Tne temperature is reduced with cooling to 1 60C 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 theresuitingsolidresinhasanEEWof lO99.AnaqueousdispersionispreparedasdescribedinExample 1, the amount of amine added is 95 % of the epoxy equivalents, and the amount of 10 lactic acid is adjusted to reach the same neutralization level.

EXAMPLE 3 - Reaction of diglycidyl ether of polyprooylene glycol with bisphenol A and ' subsequent reaction of the product with digiycidyl ether of bisphenol A ~ `
Not an Example of the In~ention. ` `~ -1 5 ' '~- ." ` ' Example 2 is repeated usi ng 620.0 9 of the diglycidyl ether of polypro~ylene glycol (EEW 317.7) prepared from a polypropylene glycol of MW 390, 571.0 g of bisDhenol A ;
and 2.9 9 of alkyltriphenylphosphonium catalyst. The mixture is heated to 1 00C. The reactor Is then slowly heated to 1 50C (1 to 2C per minute).To the reaction mixture is added 1543.8 9 of 20 the dig!ycidyl ether of bisphenol A described ;n Example 1 (8.33 epoxy equivalents) ~!~e te-nperature drops to t 10C as a result of this addition. The mixture is mixed for 5 millutes and then the temperature is slowly raised by heating (1 to 2C per minute). At 140~C an exotherm begins and the temperature rises to 1 70C. The temperature is reduced with cool;ng tO 1 60C at which temperature the reaction mixture is maintained until a sample removed shows the resin ~ r '' hasanepoxyequivalentweight~fmorethan1000.Thereactionisquenchedbycooling,and `~``r.;
the resulting solid resin iscrushed and stored. The EEW is 1082. An aqueous dispersion is prepared as described in Examples 1 and 2.
, EXAMPLF 4 - Reactir~n of diglycidyl ether of polybutylene glycol and bisphenol A and 30 sùbsequent reaction with the diglycidyl ether of bisDhenol A -Example 3 is repeated with 4t2.2 9 of a diglycidyl ether of a polybutylene glycol ~EW 250.0), wherein the Dolybutylene glycol MW ~number average) is 300; 583.8 9 of ~^
bisphenol A, and 2.0 9 of catalyst as described in ~amoie 1 t takes about 90 minuxtes until the ~eignt percenlage of epoxy ~n the mixture Is less than 0 1. To the ~eactor i5 added 1004 9 g of ~`~

~"3 :'S ;~

2l~ ~7~' the liquid epoxy resin described in Example 1. The resulting solid resin has al ~EW of 1 Q90. A
water dispersion is p-epared as dffcribed in Ex~mples 1 and 2.
;
EXAMPL~ S - Reaction of diglycidyl ether cf pdybutyl~ne glycol ant bisphenol A and subsequent reaction with diglycidyl bispi~enoI A
Example 3 i~ repea~ed with 41~.2 9 of a dic~lyciayl ether of a polybutylene glycol . :~
(~tW367.0),v~hereintheMW(number~Jerage)o~thepQly~utylene~lycolprecurso~is550 0 546.5 9 of bisphe~ol A, and 2.0 g of catalyst as ~es~rib~d ;n Exarnple ~ . It takes about 6û
m~nutes until the weight pQr~Qntage ~f epoxy in the rnixture is less than û. t . To the reac~or is added l 042.2 9 r~f the liquid epoxy -esin d-Kribed in E~ample 1. The EEW o~ the resulting resin : S :~
is 1087. An aqueous disp~rsion iS prepared asdescribed in Examples 1 and 2.

I he dispersions of Fxampl~s 1 ~o S are tested ~or pH and conductivity. The resu~
are co~npiled in r~b Table I -.. ~ .
t~. e.. mple Oxide Ae c~on pH uSJcm!~ : ~
_ _ _ _ ~ , ~ 1~ ~ propylene oxide .1 step 6.~ 1490 . ~ .
. ~ ~: . ~; ~ : _ ~, 2~ : ~ propylene oxide 2 step 6.2 1360 `
: 3~ ~ ~propyleneoxite 2step~ 60 lao 25~ ~4 ~ ~ ~ butyleneoxide2step 6.3 1154 S ~Oylene ~ e 2 step 6.2 1254 :~
. . . _ k Not a~ exa~ple o~ tne ln~en~lon ** MicrD~ie~ens / ceD.time~er EXAMPLES 2 to 5 - Cathodic Deposition of Coa~ings and Testing of Properties Dispersions prep~red in Exa~nples 2 to ~ are separately deposited on Bonder 26 phosphatiieJ stee~ panels by electrod~positior, rins-d in deioni~ed water and baked at t 75C
for 20j minutes. Depositio~ conditions a. e chosen such that the coati ng has a thickn~ss of 25 : .
microns. The Crichsen Indentation test is performed to a ~first crack~ endpoin~ ~he Salt ~ath corrosion test conditic ns ~r~ 500 hours of immersion in a 5 pe-cent st>dium chloride in wat~r -~:
35 so;ution at 55C The resultsare compiJed ;n Table 11.
....
26~ SIJ~ 5JTE SHE~
. . .

~ .
' t ,j, - . . `
. . ... .....
` .`:: `

WO 93/04104 2 ~ Pcr/US92/07234 . .

. .

~able II ~ ~
. . _. _ .. _ .... .
5 Example Erichsen mm mm Cleep Rev. Impact . .:
.
2 6.2 0.5-1.0 C 5 3 5.7 < 0.5 . ~`
4 7.6 ~ 0.5 10 :
1 o .. _ . . . _ ~ .
7.5 < 0.5 20 ~:

EXAMPLE 6 - Reaction of Diglycidyl ether of Bisphenol A, diclycidyl ether of polypropy!ene `
l S glycol~ and ~, BispnenolA
Not an example of the invention ~
The following amounts of raw materials are charged into a 1 liter glass reactor: ~ ;
382.7 9 D.E.R.~ 331 epoxy resin (EEW = 186.9~, 200 9 of D.E.R.~ 732 epoxy resin, the diglycidyl 20 ether of a polypropylene glycol, (EEW = 318.5) and 217.3 9 of Bisphenol A. The mixture is heated under stirring and a nitrogen purge tO 90C and then 0.71 9 of a trialkylphosphonium `
catalyst is added. The temperature is gradually increased. At 1 40C the exotherm begins and the temperature increases to 180C. The temperature is then decreased with cooling to l 70C ~r~
-and maintained for 45 minutes, until a sample of the reactor contents shows an EEW of 1050.
The resin is cooled, crushed and stored.

The resulting resin is converted into an aqueous dispersion using the procedure `
described in Example 1, with the exceptions that the crosslinker is as described in US Patent 4,104,147,moreparticularly70wt%solutioninMlBKofan3:1:3adduct~basedonmolar ;
30 quantities)oftoiuenediisocyanate,trimethy!c -opaneandethylhexanol.Additionaliy, 10 9 of dibutyltindilaurate cur~r~ calalyst is added t~ e resin crosslinker blend, just oefore aispersing it into water.

Aftèr strioping, tne aisDerslon is dilutea tO 20 wt ?o solids and used for 35 eiectroae,oosltlng an unP~9mented coallng unto ~onder 26 panels and unto degreasea untreated steel panels. The coat~ngs are cured for 20 mi nutes at l 90C. 3eDosition conr ltions are cnosen in sucn a way thas the iinal film thickness of the cured films is 20 um.

: .',.`., :

W O 93J04104 2 ~ 3 P~r/US92/07234 EXAMPLE 7 - Reaction of Bisphenol A with diglycidyl ether of polypropylene glycol, and 5 subsequent reaction with Bisphenol A diglycidyl ether Not an example of the invention The following amounts of raw materials are charged into a 11 glass reactor: 200 9 of D.E.R.* 732epoxyresin,thediglycidyletherof polypropyleneglycol, (EEW= 318.5) and 217.3 g of bisphenol A. The mixture is heated under stirring and nitrogen purging to 90~C after which 10 0.71 9 of a trialkylphosphonium catalyst is added. The reaction mixture is gradually heated to ~, 170C, and maintained for 50 minutes until analysis of a sample of the reaction mixture shows anepoxycontentlessthanO.l wt%.~87.2gof D.E.R.~ 331 epoxyresin(EEW- 186.9~are .-added, causing a temperature drop to 110C, after which the mixture is reheated to 130C. The exothermic e~fect of the continuing rea~tion raises the temperature to 170C. The reaction is 15 continued at that temperature for 20 minutes until analysis of the resin gives an EEW vaiue of 1072. The resin is cooled, crushed and stored.

The conversion into an aqueous dispersion, the electrodeposition of the resulting clear coating and its curing are performed in the same way as described in Example 6.

EXAMP!E 8 - Reaction of diglycidyl ether of Bisphenol A diglycidyl ether of polypropylene glycol and Bisphenol A
Not an exampl~ of the invention Using the procedure as described in Example 5 a resih is prepared. The reactor is 25 charged with 389.2 9 of D.E.R.~ 331 epoxy resin,200.0 9 of the diglycidylether of a polybutyleneglycol(EEW= 368.12)and210.8gofbisphenolA.TheresultingresinhasanEEW
of 1050.

Conversion into an aquec us dispersion, electrodeposition and curing are 30 performed in the same manner as described in Example 6, except for the amount of .
neutralizing acid, which is 5 % higher.
~ . .
EXAMPLE 9 - Reaction of Bisphenol A with diglycidyl ether of polybutylene glycol and subsequent reaction wlth diglycidyl ether of BisDnenol A

'~ `
-28- ~ `

WO 93/04l04 2 1 1 ~ 7 9 ~ Pcr/us92/o7234 '':` ~.

~ .
Using the procedure described in Exam~le 6, 200 9 of the diglycidylether of a polybutyleneglycol (EEW = 368.1 ) and 210.8 9 of bisphenol A are charged into the reactor and 5 the reaction proceeds. In the later stage of the reaction 389.2 g of D. E. R. ~ 331 epoxy resi n 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 Example 6, except for the amount of neutralizing acid which is S % higher. .

Results of pH and conductivities of the clear dispersions of Examples 6-9 at 20 wt % solids are listed in ~ ~le lll. Results of reverse impact, Erichsen tndentation, Salt Bath `~ -~
immersion test and sc~ . ;pray are also listed. The salt spray test is performed according to ASTM `
B 117 for 300 hours on degreased untreated steel panels coated with the ~ured panels. Tests performed on the cured clear coatings are shown in Table IV.
Table III
......... "': .
Example Oxide Type ~rocedore pH Conductivity :

6* ~~: propyleneoxide 1step 6.6 1790 _ . ... _.. _ . r 20 7* ~ propylene oxide 2 step 6 4 1850 :8~ : butyleneoxide 1 step 6.2 1660 ^ 9~ ~ butylene oxide 2 step 6 0 1484 Not an example o the inven ion ~ ~ _ ** Microsiemen~slcentimeter Table IV
,,, .~
act ¦ Erichsen ¦ Immersion ¦

6* 116 8.8 3.2 , . . . -7* > 160 9.1 2.0 4.5 ~ , . _ . . . . _ .` 8* 100 8.7 3.5 , _ _, . . . ..
9 i 160 9.2 1 .0 2.0 Not an example Ot the inventlon '~` ''"'`' -~.

: ~.

W O 93/04104 2 1 14 ~ PC~r/US92/07234 ~.,.

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 5 bisphenol A.
325 9 (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 Ol 1) 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 1 . and 2 degrees C per minute while contents are stirred. When the reactor temperature reaches 10 120C, l .1 9 of alkyltriphenyl phosphonium catalyst are added. Heating of the reactor is continued until a rnild exotherm is observed to begin at around 1 50C, at which time the : .
external heating is discontinued. Once the exotherm finishes and the temperature returns again to 160C, 3,240.1 9 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 1 00C, and an additional 2.4 '~
grams of alkyltriphenyl phosphonium caealyst are added. Heating is continued until the~ ~ ~
beginning of an exotherm is obseNed. At this point ehe external heating is again discontinued. ~ '`
After exotherm cool-down, and flaking, the epoxy is analy~ed and found to have an EEW of - 759.7, a Mètler solftening point of 89.4C, and a melt viscosiey of 1.81 Pa.s at 150 C.

EXAMPLE~ Preparation, application and testlng of a powder coating 840.4gramsof the flaked resin of E)tAMPLE 10, 259.6grams of D.E.H. 81 (commercially available phenolic OH functionaî hardener commonly used in pipe and functional powder coatings), 600 grams of TiO2, 200 grams of BaSO4, and 100 grams of CaCO~
25 - are~ premixed mechanically in a lab mixer for 3 minutes at 600 RPM. This dry mix is then ~ ``
completely meit- homogeni~ed by feeding it through a ZSK 30 twin screw laboratory extruder `
at a temperature of 90C and a screw speed of 300 RPM. The e~trudate is cooled by passing it between two water cooled rolls and the resulting sheet is then flaked. The flakes are ground on a lab grinder until 100% will passthrough a 100 micron screen. This final powdet is bagged 30 and kept cool and dry.
6 mm thick cold rolled steel panels are cut to nominal dimenslons 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 c~rculating air oven which has been set to 235QC. After Dreheating for 20 minutes, the Daneis are removed from the oven and hung in a sDray booth.
35 The panels a~e electrostatically sprayed to an e5timated thlckness of 350 mlcrons wilh the `
oowcier coat!ng. After coating the paneis are returned to the 235 deQree oven for a l minute .

30.
:, ~ : .. `

WO 93/04104 2 1 1 ~ 7 ~ ~ PCI /US92/07234 ~

post cure, after which they are quenched by immersion in cold water. The resulting coatings are hard and glossy.
, .
The flexibi I ity of the coating is tested by bending the coated panels around an 18 mmdiametermandrel inaccordancewithDlN35571 flexibilitytest. 10panelspreparedas 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.
:~
EXAMPLE 12 - Reaction of diglycidyl ether of polybutylene glycol with bisphenol A and subsequent reaction of the produ~t with diglycidyl ether of bisphenol A.
404.1 grarns ~ 1.609 eRoxy eq) of the diglycdyl ether of the 330 Mw poly~utyleneglycol and 494.6 grams of bisphenol A (4.338 phenolic OH eq) are charged to a 2 liter reactor. A ; -~
15 gentle nitrogen purge is started over the contents and the temperature is raised at a rate between 1 and 2 degrees C per minute while contents are stirred. When the reactor temperature reaches 120C, l gram of alkyltriphenyl phosphonium catalys~ is added rieati ng of the reactor is continued until a mild exotherm is observed to begi n at araund 150C, at which time the extern. leating is discontinued. Once the exotherm finishes and the temperature 20 returns again to 160C,601.4 9 (3.36 epoxy eq) of diglycidyl ether of bisphenol A with EEW of 178.6 are charged to the reactor. The reactor is agai n heated at a rate of 1 to 2 degrees per mi nute um: i the temperature reaches 120C at which point an additional 1.65 grams of alkytriphenyl phosphoniurn catalyst are added. Heating of the reactor is continued until an exotherm is observed at around 150 degrees. At this point the external heating is discontinued 25 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 Metler Softening Point is determined tobe 104.1Candthesolutionviscosityat40wt% solidsindiethyleneglycol monoblJtylether Is meas~ eci to be l 914 cSt.

EXAMPLE 13 - Formulation application, and testing as a can coating 80 grams of the advanced resin of EXAMPLE 12 are dissolved i n l 50 grams of a soivent biena consisting of 50 Darts Dowanol PMA, 10 Darts of 2-butanol and 40 parts of Solvesso 100. '0 grams ~soiids) each of Phenodur PR 285 and Bakelite '00 kommerclal vhenolic 35 reSoie crosslinkers) are added to the advanced resln solution. l ~ram (soiid) of Dhos~horic acid s added to accelerate the cure. The formulation is ailowed to age for 24 hours at 40C and is -31 - -:

WO 93/04104 ~ 7 ~ ~, PCTtUS92/072~

then reduced with the solvent blend described above until a ASTM D445 viscosity of 250 mPa.s : :
is reached. The soiids content is measured to be 38 wt % .
~ .
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 ti n plate (both available from Rasselstei n AG) which have been degreased by rinsing with acetone. A wet application of between 20 to - 40 microns is chosen such thatdry film thickness of 5 to 6 microns is obtained. The coated tin .
plate panels are placed in a circulating air oven preheated to 200C for a cure time of 10 minutes. The coated tin free steel panels are cure at 280 for 28 seconds.
..'; ~:-To test the performance of the coati ngs, 2 cm high asymmetric cans with 5, 10, 1 5, ~ -:
and 20 mm radi us corners were drawn from the coated tin free steel and ti n plate sheets. In `
15 each case, perfect coa~ing integrity on all corners and edges is maintained throughout the - ~
drawing process. The drawn cans are further tested by exposi ng them to water at 1 29C. The ~ : -exposuretimeis30minutesforthetinplatecansand90minutesforthetinfreesteelcans. In each case, the integrity of the coating is maintained during the exposure and no blushing or blistering is observed. ~ --32- :~

Claims (10)

PATENT CLAIMS:

1. Flexibilized epoxy resin comprising the residue of A. one or more polyglycidyl ethers of a water or di- or trihydroxy substituted C1-6 hydrocarbon initiated polybutylene glycol;
B. one or more polyaromatichydroxy compounds; and 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 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 ofpolybutylene glycol or at 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 polyaromatichydroxy compound through the reaction product of a glycidyl ether moiety and an aromatichydroxy moiety;
wherein the mole ratio of polyaromatichydroxy compound to polyglycidyl ether of polybutylene glycol is two or greater; 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 according to Claim 1 wherein the epoxy resin contains at least 5 percent by weight of polyglycidyl ethers of polybutylene glycol.

3. Flexibilized epoxy resin compositions according to Claim 2 wherein the glycidyl ether of a polybutylene glycol corresponds to the formula:

the polyaromatichydroxy compound corresponds to the formula:

and the polyglycidyl ether of a polyaromatichydroxy compound corresponds to the formula:

wherein:
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;
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;
T is independently in each occurrence a direct bond or the moiety ;

Z is independently in each occurrence oxygen or ;

X is independently in each occurrence a C1-6 alkyl moiety;
R1 is independently in each occurrence hydrogen or a C1-4 alkyl moiety;
a is independently in each occurrence a positive real number of about 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;

with the provisio 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.

4. Flexibilized epoxy resins according to Claim 3 wherein the resins comprise compounds corresponding to the formula wherein:
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 ;

E is independently in each occurrence a moiety according to one of the formulas or 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;
T is independently in each occurrence a direct bond or the moiety ;

R1 is independently in each occurrence hydrogen or a C1-4 alkyl moiety;

Z is independently in each occurrence oxygen or ;

X is independently in each occurrence a C1-6 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;
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 futher compriseD. cationic terminal moieties comprising the reaction product of a nucleophile and the glycidyl ether moieties.

6. Flexibilized advanced epoxy cationic resin compositions according to Claim 5 wherein the nucleophile is a monobasic heteroaromatic nitrogen compound, tetra(lower alkyl) thiourea, a sulfide corresponding to the formula:

an amine corresponding to the formula:

;

or a phosphine corresponding to the formula:

;

wherein:
R6 is independently in each occurrence lower alkyl, hydroxy lower alkyl or two of R6 may combine as one 3 to 5 carbon atom alkylene radical thereby forming a heterocycloalkylene moiety;
R7 is independently in each occurrence hydrogen, hydroxyalkyl, lower alkyl, aralkyl or aryl;
R8 is independently in each occurrence hydrogen, lower alkyl, hydroxy lower alkyl, the moiety ;

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 lower alkyl or aryl;
R10 is independently in each occurrence a C2-10 alkylene group;
R11 is independently in each occurrence lower alkyl.

7. A coating composition which is suitable for 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.

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

9. A process for preparing flexibilized epoxy resins comprising A. reacting a polyglycidyl ether of a di- or tri- hydroxy C1-6 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 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 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.

10. A process according to Claim 10 wherein the polyglydicyl 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 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 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 molecular weight is reached.