CA1113643A - Method of water-solubilizing high performance polyether epoxide resins, the solubilized resins and thermoset, hydrophobic coatings derived therefrom - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Hydrophobic, thermoset resins having highly desirable properties in coatings applications can be prepared from water-thinnable base salts of novel acidic, polymeric esters made by reacting orthophos-phoric acid with hydrophobic, nominally-difunctional polyether epoxide compositions having average epoxide equivalent weights of from 172 to 5500. The base salts are thermally decomposable to yield resins which are rapidly self-converting if methylol or alkoxymethyl substituted epoxides are included in said compositions.
The functional groups responsible for water solubili-sation are utilized in curing of the resins. The inven-tion provides a method of utilizing hydrophobic, high performance polyether epoxide type polymers in aqueous coating systems having relatively high abilities to wet non-polar surfaces. Wetting properties of the systems may be varied by choice of the organic radicals included in one or more of the epoxide components of the poly-ether epoxide composition employed.

Description

The invention is a water-thinnable resin compo-sitionJ a method of preparing it and coati~gs derived from it.
The composition of tha invention is a mixture of base-neutralized reaction products of H3PO4 with polyether apoxides of foregoing formula (a) or (q) and, optionally, any of various other types of mono~ or polyfunctional epoxides.
The preferred method of the invention is to I0 react the polyether (El) and, optionally, other (E2) epoxides with an orthophosphoric acid source material and to neutralize the resulting product with a base, preferably a fugitiv~ base. However~ the invention also comprises the method o~ preparation in which separately prepared El and E2 reaction products with phosphoric acid are combined. If the base is a fugitive baseJ
such as ammonia or a volatile amine, the water-thinned~
neutralized resin can be converted to a water-insensi-tive, high performance, thermoset resin by evaporating tne water, heating to disrupt the ammonium salt groups and drive off the ammonia (or amine) and curing. Con-ventional curing agents capable of reacting with acidic and/or alcoholic hydroxyl groups may be incorporated with the uncured resin.
~he term "volatile" means removable, by heat-in~ at ambient pressures, to such an extent as not to have an intolerably detrimental effect upon the rate of curing ox On the properti~s of the cured resin.

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18,224B-F -1~

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3~;~L3 ~ .~e am~onia (or arnine) dr.iven of:E during or subsequent to ev~poration of water from the uncured resin cc~n readily be recovered as such or as a non~volatile acid salt, by kncwn methods.
The coatings of the invention a.re those forrr.ed on various substrates (preferably metallic) from aqueous dispersions of the preceding compositions.
Thus, in one aspect, th~ present inven-tion provides a prccess ~or making water-thLnnable, baæ-neutralized acidic resins which are convertible to hydrophobic, high performance, thermoset resins, said process comprising:
(I) reacting orthophosphoric acid with (1) a polyether epoxide resin El consisting essentially of molecules, each of which is of the formula (a) CH2-C-OE12-O- ¦ Q-O-CH2-C-CH ~--Q-O-CH2-C-{~12 R L Rl n or.of the formula R l OH O

(q) R ~ -O-CH2 C--CH2-0---Q-O-C~I2-C-CH2-O- Q CH2 C, CH2 l Rl - n R

; wherein Q, independently, in each occurrence, is n is an integer of from 0 to 40, r is zero, 1 or 2 and, independently in each occurrence, . .

.~. 2 .L~ , :: . . ~ . . . .
.:.: . , , .3~43 R is H, methyl or ethyl, is -Br, -Cl or a Cl to C4 alkyl or c~lkenyl group, R3 is a Cl-C4 alkylene or alkenylene O
.~ gr~Up~c(cF3)2~ -C- , --S02-, -S , -O- or a ~; valen oe bond, R4 is Br, -Cl or a Cl -to C4 alkyl or alkenyl group, and R is H or alkyl of 1 to 12 carbons;
and, optionally,

(2) E , a vicinal epoxide, other than one of formula (a) or (q), which has an EEW (epoxide equivalent weight) within the range of from 90 to 2000 and i.s i~ convertible to a water-dispersible material by reaction wit~ orthophosphoric acid : and neutralization with a base, said reaction being carried out by contacting ~, and, optionally, E with an orthophos~horic acid source material and from 0 to about 25 molecular proportions of water per molecular proportion of H3PO4 prnvided by said source material until the fraction of the oxirane groups in E and, optionally, E converted is at least sufficient to render the resulting mixed product water-thinnable when oontacted with a base, the amount of orthophosphoric acid included as such in said source material, , ~ ~ - 3 -~: .

, . .
or obtainable ~herefrom by hydrolysis, b~ing such as to provide at least 0.3 P-OH groups per oxirane group, and the mole ratio of s; to E epoxides being frorn 0.1 to 100 when ~' 5 E~ is present, ~ and .~ (II) contacting the resulting reaction praduct with ~ .
at least enough of a base to render it water-. -thinnableO
In one aspect/ the composition of the invention is a resinous mixture, produced by t'he reaction of phos-phoric acid and El and, optionall~, E2, as above defined, which is water-thinnable when neutralized with a base.
-~ In another aspect~ the composition of the inven-.` 15 tion is the water-thinnable product obtained by contacting : said resinous products with a base~
A~ueous dispersions of the neutrali~ed products ~- constitute a preferred embodiment of the composition of `' the invention.
~:~ 20 The neutralized, epoxide/aciæ reaction products : of the present invention may be more precisely defined as a water-thinnable, resinous phosphate composition ' comprising:
(A) re~in molecules, each of which is derivable by conversion to 1,2-glycol- or beta-hydro.Yy ,i , . .
~ phosphomonoester groups of the oxirane groups .-~ in an El epoxiae represented by one of formulas (a) and (q), the average EEW of the epoxide ~' molecules xom wh.ich the resin molecules are .

: 18,224B-F ~4~ ~:
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derivable beincJ from 172 to 5500, optionally, o-ther mo:lecules, each of which is derivable by conversion to 1,2-ylycol- or beta-hydroxy phosphomonoester groups of the o~irane yroups in E , a vicinal epoxide other than those oE
Eormulas (a) and (q), having an EEW within the range of from 90 to 2000, the mole ratio of said El-derivable molecules -to said E2-cleriv-able molecules being within the range of from 0.1 to 100, and the number ratio of glycol to monoester groups in each of said types of molecules being with the range of from zero to 18;
5~ (B) from 0 to 85 parts by weight of ortho phosphoric acid (H3PO4) per 100 parts by weight of said El- and E2-derivable molecules, ` and (C) a base~ in such amount that at least enough of the P-OH moieties in said El and E -deriv-able molecules are salified thereby to render them dispersible together in water.
In a preferred type of the prececling composition, those molecules not derivable frc~ epoxides of formula (a) or (q) are derivable frc~ E2 epoxides, as above de-fined, which comprise benzene rings substituted with ` methylol or lower alkoxymethyl groups (i.e., R-O-CH2-groups in which R is an aIkyl group of 1 to 4 carbons or an alkenyl group of 2 to 4 carbons).
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In another preferred typa of the preced,ing composition, the molecules not derivabl~ from a~ El epoxide are derivable from an ]E2 epoxide consisti~g of epoxy novolac molecules.
The base componen^t oE the above defined compo-sitions preferably is of fugitive character.
As employed herein, the term "water-thinnable"
means that the product so designated forms an essentially homogeneous solution or dispersion, upon being diluted with a substantial proportion of water~ and the result-ing dispersed product does not "settle out" or otherwise dPtrimentally alter at such a high rate that the disper-~ion is impracticable ~or use as a coating.
The mixtures which constitute the composition may be formed in either of two ways. The El and E2 epoxides may be co-reacted with a phosphoric acid source ma~erial or the products obtained by separately reacting the epoxides may be mixed (beore or after neutralization with the same or different bases).
The latter mode of preparing the compositions is considered as another (process) aspect or embodiment of the present invention. That is~ the invention also comprises combining saparately formed El/~3PO4 and E2/H3PO4 reaction products and sufficient base to render ,, the combination dispersible in water.
~he following e~bodiments of the invention are most preferred as ha~-~ing part~cular merit for coating appli~ations, , 18,224B-F -6-.

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(1) The proauct of the ~oregoing process wherein El is a diglycidyl ether, as defined in formula (a) above, derivable from adductive polymerization of bis-ph~nol-A with a diglycidyl ether of bis~phenol-A, i.e., wherein R is C~13-C-C~3 and r is zero.
(2) A product o e~odiment (1) which has been made water-thinnable by neutralization with ammonia . or an amine;

(3) The neutralized product of embodiment ` 10 (2) when thinned with water to a resin content of 50 . weight percent or less.
; (4) A the~.^set resin coating prepared from the water-thinned product of embodiment (3).
(5) The product of the foregoiny broadly defined process wherein El has an EEW o~ less than 3200.
(6) The embodiment of the foregoing bxoadly - defined process in which the overall ratio of acidic `~ hydr~xyls to oxirane groups is within the range of from :~ 0.4 ~o 1Ø
(7) The embodiment of the foregoing process in which the amount of H3PO4 provided to the reaction is 1 part or less by weight per 100 parts of E .
(8) The embodiment of the foregoing broadly : defined process wherein the phosphoric acid i5 charged to the reactioD as 70 to 90 weight percent, acIueous, .. .. .
~3PO4 The cured resin of Pmbodiment (4) above may be derived from an aqueous composition of the invention in which the water-thinned) neutralized epoxide/H3P04 18,224B-F ~7~

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reaction product is the sole resinous component or from similar compositions in which other water-clispersible resins~ reactive diluents and/or curing agents are also present. In either case, curirlg may be catalyz~d by : 5 such known agencies as chemicals, ultrasonic vibrations, heat, high energy wave or particle radiation, etc.
The El typ~ of epoxicles represented by formula (a) may all be described as resins. A few of the lower epoxides, such as the diglycidyl ether of bisphenol-A, are available as pure, crystalline solids. However, most DGEBA-type epoxides are not ordinarily available as pure compounds, as a consequence of the practical methods employed in their manufacture. Thus, DER-331~, a less expensive form of the diglycidyl ether of bis-phenol-A, is prepared through a two-step reaction Of epichlorohydrirl with bisphenol-A. The product of this reaction includes not only the desired diether but also , ~ -. .
(in minor amounts) by-products such as C-CH-CHz-O ~ , ~ ~ ~ CH ~ CH

~H2 ~he presence of such lmpurities, of the t~pes ~ and in the amOunts ordinarily present have no substantial ; deleterious effect in the products of the pxesent inventionO
Any of the epoxides of ormula (a3 having an ~ ~ EEW of less than 5500 can be prexeacted with a phenol `^ 25 (as above defined), in such amount as to convert that 18,2Z4B-F -8-.D .
. ~ , .. ~ .

3~3 ., ; epoxide to a resin having an EEW not in exce~s of 5500 and comprising a corresponding proportion of product molecules representable by formula (p).
The reaction is usuallly carried out by dissolv-ing the El epoxide(s) in the medium (when such is employed), adding the acid source material and such water as may be , required to utilize that matPrial or to give the desired product compositionJ and refl~xing the mixture at a pre-selected temperature (and pressure) until the desired degree of oxirane conversion has been attained. The reaction mixture is cooled, neutralized with the base selected, diluted with water (often in an amount equal to the weight of solids present) and stripped.
, Phosphoric acid source materials which may be ,~; 15 employea in the El/acid reaction include 100 percent orthophosphoric acid, the semihydrate 2H3P04 ~20 and aqueous solutions containing at least 18 weight percent H3P04 ~1 mole H3P04 per ~5 moles of water). The various condensed forms ~polymeric, partial anhydrides) of phos-. phoric acid, e.g.~ pyrophosphoric acid and triphosphoric acid may also be used.
When the acid source material is of the con-densed type, su-fficient water should bs supplied, at q;~` som~ stage prior to curing the resinous end-product, to ensure that no substantial proportion of P-0-P links are Ieft in the cured resin.
~, .
Orclinarily~ aqueous phosphoric acid solutions~
particularly 70-90 percent solutions, will be preferred.
~- When a condensed form of phosphoric acid is utilized as , . .

~18,2~4B-F 9~

the source material, the s~age in the process at which P-O-P hydrolysis is effected will depend on whether or not minimization of water cont:ent during the reaction is desired. If a condensed sourc~ material is to be fully utilized as H3PO~ in the reaction, sufficient time should be allowed for complete P-O-P hydrolysis to occur~
: The epoxide/acid reaction can be carried out with the neat reactants but it is preferred to employ an e~fectively inert reaction medium. Exemplary o~ sol-vents which are suitable for this purpose, in order of . decreasing preference, are the following:
(1) mixtures of acetone with methylene chlorias :~ comprising 25 or less waight percent of the latter solvent, ~5 t~) ketones such as acetone and methyl ethyl ketone~
~` (3) cyclic ethers such as dioxane~ .
(4~ linear ethers, such as glycol ethers~
(5) esters, such as lower alkyl acetates, (6) mixtures of lower alcohols and chlorocarbons such as methylene chloride, (7) lower alcohols~ and (8) chlorocarbons, such as methylene chloride.
~hè parameters which predominantly determine the water-thinnability of the (neutralized) El/acid . ~ , .
reaction product are the EEW o~ the El epoxlde, the .: P-OH to oxirane ratio, the water to P-OH (H3P04) ratio, the solubility of water in the reaction medium, tempera-. ture and contact time~
. . , ' , .. ~ 18,224B-F -10-~` ' ' .

t;~

~o be water-thinnable, when neutralized, the reaction product must have at least a minimal content of phosphomonoester groups and this imposes an upper limit of 5500 on th~ EEW of the El epoxide and a lower S lLmit of 0 3 on the ratio of P-OH groups (provided by the acid source material) to oxirane groups. It is ; also essential to water thinnability that the ratio of glycol groups (from adduction o~ water with oxirane groups or hydrolysis o~ phosphodiester groups) to phos-phomonoester groups is not higher than 18 to 1. This in turn requires that the mole rati~ of water to H3PO4 in the reactants is not higher than 25 to 1.
The extent to which water enters into the reaction depends not only on the water to acid ratio but also on the activity of the water, which in turn depends both on the nature of the reaction solvent and the temperature. As a yeneral rule3 the activity o~ the water will be lower in poor solvents for water and at lawer temperatures.
Adduction of P-OH with oxirane groups appears to proceed fairly rapidly in less polar solvents and, in such solvents, formation of ~,~'-dihydroxy phospho-diester groups OH O OH

OH
~` 25 occurs to a substantial extentS at least in the early s~ages of the reaction. If water is absent or has a low acti~ity in the solvent, the oxiranes may be pre-dominantly converted to such diester groups and the ;:
18,224B-F

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~' ' E molecule~ may be linked together by the diester ; grOups to such an extent that gelling results.
The diester groups ar~ readi~y hydrolyzed (to "glycol" and monoester groups) and therefore generally do not constitute an important component of the final .~ pxoducts derived ~rom reaction mixtures in which the ,; activity of water is substanti.al. Furthermore, in the : more polar solvents, acid-catalyzed adduction o~ water with oxirane groups appears to compete quite effectively with P-OH adduction.
Both adduction and hydrolysis reactions of course proceed more rapidly at higher temperatures and shorter contact times are accordingly required to attain a desired degree of oxirane conversion or to reach an .~ 15 aquilibrium condition. If tha activity of the water present is markedly higher at a more elevated tempera- -ture~ the proportion of "glycol" groups in the product may increase accordingly.
As a consequence of oxirane conversion directly to glycol groups, free H3PO4 will generally be present in the reaction product~ even when the P-OH to oxirana ratio in the reactants was substantially less than 1.
~wever, the presence of the free acid (as a base salt) in the neutralized product does not ordinarily have a ~S serious detri.mental effect on the dispersibility of the -.- product in water. Thus~ a water dispersible.product : can be obtained in some cases even when the amount of :~ the acid source material employed in the reaction is ~: so high t~at as much as 85 parts by weight of H3PO~

': ' .~18,224B-F -12-`i 3~

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per 100 parts of the El d~rived resin molecules will be present in the product. However, such high acid contents result in poor hydrolytic stability in the cured coating. Of course, high acid contents can be l~wered to tolerable levels by extraction, preferably before the product is neutralized.
: The water-thinnability of the El/acid product has been found sensitive to thle nature of the solvent it is associated with when the neutralized and water-- 10 -diluted reaction mixture is stripped. The reaction solvent best suited to formation of a product of a desired composition may not be the best medium from which to form the aqueous dispersion. However, the reaction mixture may be stripped before (or even after) neutraliæation and dilution with water and replaced by a more suitable solvent~ Methyl ethyl ketone has been found ad~antageous for the latter purpose. Alternatively~
by using acetone including a minor proportion of methylene chloride as the solvent, very good results are obtained both in the reaction and the dispersion steps.
Pre~erred reactant ratios and conditions for the El/acid reaction are as follows: acid source material, aqueous 70 percent to 90 percent H3P04; amount of acid source material, such as to provide from 0.8 to 1.2 P-O~'s . .
per oxirane; reaction temperature~ within the range of - from 110 to 130C; and contact time3 within the range of from 3 to 6 hours. Supra-atmospheric pressures, at least equal to the autogenous pressure of the reaction mlxture, of course must be maintained at temperatures 18~224B-F -13- ~

- ~ :
-&~ 3 above the boiling point of the solvent at atmoqpheric pressur~. (Temperatures of up to about 150C may he employed.) The foregoing summary is generally applicable `~ 5 to the reaction of E2 epoxides with phosphoric acid source materials to form products which will be water--thinnable when neutralized. It i9 also generally applicable to co-reactions of El and E epoxides with PO4 (etc.)~ HoWever, it is desirable to employ lower reaction temperatures (and/or to moderate the reaction in other ways) when the epoxide (E2 or El) tends to readily polymerize a~d/or is substituted with such in-herently reactive ~unctions as methylol- or lower alkoxy-~ethyl groups.
It may also be noted that most o~ the E2-type ,~, , .
epoxides which will be used have substantially lower EEW's than the most important El epoxides (those for which the average value of n, in formula (a) or (q), is 9 or more). Consequently~ it may not always be nec-essary to stay within the various ratio limits sat out above or the El/acid reaction and productsJ when using an E epoxide alone. In general, however, the best dis-persions, of E2 products or of mixed El and E2 products, will be obtained by staying within those limits.
~ 25 The base constituent of the neutraliæed~ mixed - ~ El and E acid reaction products preferably consists of one or more fugitive bases~ That is, those bases present are volatile and dissociate ~rom the acid (free acid or phosphoester P-OH) groups upon heatin~ the ,~,. .
~ 18~224B-F -14-~ .

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salified product to a temperature ~qual to o ~ lowar than the required cure temperature (but higher than the maximum kettle tempPrature attained during stripping).
Ammonia and amines are exemplary o~ such fugitive bases.
The preferred bases are amines, particularly thos~ of the formula NR3~ wherein each ]~ is H, methyl or ethyl, independently, except that not more than one R ls H.
The most preferred base is triethylamine.
To facilitate understanding of the further l~ discussion of the present process invention that follows herein, the natures of the El and E2 epoxides employed will first be disclosed in greater detail, Suitable E epoxides for the practice of the presant invention are defined by ~ormulas (a) and (q) earlier herein, Preferred among such epoxides are those in which Q, in all occurrences~ is i.e., El is preferably a nominally difunctional epoxide '- of the formula CH2-C-CH2-0 ~ ~3 ~ 0-CH -R-CH -0 ~ ~ 2 - O n O-CH2- -CH2 , or a nominally monofunctional monoepoxide Rl derivable thexefrom by l:l adduction with a phenol of the formula 20 ~ r 2 R ~ OH, wherein R ~ r and R are a~
above defined,, :' 18,224B-F -15-~, ~

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Particularly preferred are El epoxides o~ the foregoing formulas in which Q, in essentiall~ all occur~
rences, is either R2 R2 R ~ or ~ R3 -r R2 ~ ost preferred are E epoxides in which Q, i~ essentially all occurrences, is r r . The individual epoxide of the forego; ng type 10 presently considered to be best for the practica of the invention is DER~-667 (or equivalent DGEBA resins for which n (in for~ula (a~) is within the range of from 10 to 13 (EEW from 1500 to 2000).
~he most widely used resins of the foregoing : 15 type are DGEB~ (diglycidyl ether/bis-phenol-A) resins, i.e., polyeth~er diepoxides der.ivable from the polymeric adduction of'bisphenol-A

( ~0 ~ C - ~ OH) with the ~ .
18,224B-F -16-.', ;''`

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diglycidyl-ether of bisphenol-A

~2C-C-C-O ~ C ~ O-C-!C-C~ he diglycidyl ether may be preformed by reacting two mole-cules of epichlorohydrin with one molecule of the bis-phenol-A in the presence of a base, such as sodium hydroxide. Classically, however, the latter reaction is carried out in such a manner that resulting di-ether molecules react in-situ with bisphenol molecules to produce .
the DGEBA resinO
In the latter case, the reaction product tends to be a mixture consisting predominantly of polymeric .~ species of different molecular weights corresponding ; to different values of n in the following idealized formula:

H~C -CE~-CE2 0 ~_ C

,H3 ~ 0-CH2-CH-CH2 By reason of including some monofunctional epoxide species, such mixtures exhibit average epoxide functionalities . ~ .
- of somewhat less than ~o.
The epoxide equivalent weights giv~n subsequently in the examples herein for the preceding types of epo~ides ' 18,224B-F -17-~ , .
:
:

3~ 3 ., are generally somewhat higher than the theoretical values for the nominal compoundsJ for the reasons explained above.
rrhe practice of the present invention is not restricted to the use of one type of E epoxide at a tLme or to such epoxides in w~lich all Rl, R , R3 or R20 groups are the same throughout the molecule. Two or more distinct El epoxides may be combined in a single reaction product with phosphoric acid. Similarly, a given El epoxide may comprise as many different kinds J~',, o~ Rl groups (H, -C~3 or -C2~5), R2 or R4 groups (-Br, -Cl or -CH3), R3 groups (Cl-C4 alkyl or alkylene, -SO2-or -0-) or R ~roups (H or C1-C12 alkyl) as it is synthetically feasible to incorporate in individual - 15 molecules of -the formulas given in the foregoing broad definition of the invention.
Thus, for example, polyether diepoxides may be formed by using a mixture of epichlorohydrin and methylepichlorohydrin in place of either chlorohydrin ~; 20 alone, in well known methods of synthesisg such as are described in Handbook of Epoxy Resins; (-~h 2) Lee and eville; McGraw-Hill3 (1967)~ Similarly~ mixtures of different bisphenols may be employed in well known . ~ procedures for reacting an individual bisphenol with , . .
an epichlorohydrin or with a diglycidyl e'her of the same or a different bisphenol~
`~ Few, if any~ commercially available DOE BA-type ,,~ resins are derived from bisphenols other than bisphenol-A
'` (as such, or substituted with bromine or chlorine) or r. ,~ ' . .
... .
, ~ 18,224B-F
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from chlorohydrins other -than epichlorohydrin itself.
That is, the commercially available DGEB~--type resins axe those of the preceding ge:neral formula for E in which Rl is H, is either 0 or is 2 and ~2 is Br or Cl, and R is ~CH3)2C ~ . Exempla:ry of such commercial ~"~ DGEBA resins, which are prefe:rred for the practice of '~ . the present invention~ are the following (manufactured by The Dow Chemical Company):

TABLE A

Viscosity;
: 10 Theoretical cps @25C
Value of n or Corresponding to (Duran m.p.) Desiqnation M ~ = 2xEEW EEW ~ C
DER~-332 0 172-6 4000-5000 if~ -542~ 0 330-80 (51-61) j ~ -337 ~_0.5 230-50 semi-solid -6~0 r- 2 ~25-75 (65-74~
-661 2-3 475-575 (70-80) ., 20 -662 3-4 575-700 (80-90) ,. -664 5-6 875-975 (g5-105) 67 10-13 1600-2000 (113-123) -668 13-23 2~00-3500 (120-1~0) , ~ -669 23-38 3500-5500 (135-155) -68~ f-90 ~ 13000 --~' otes: ~f Epoxide Equivalent Weight , ~ ~ Prepared from tetrabromo-bisphenol-A
Molecular Weight ::
The epoxide functionality of DGEBA resins is 30generally le~3s than the theoretical value of 2 and the ' .
18,224B-F -19-,~:

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3~3 ,i actual values of n for th~ resi~s llsted above would be lower than the theoretical va:Lues calcula~ed for molecular weigh~s equal to twice the EEW's given.
According to Lee ~ ~eville (loc cit) J a typical DGEBA resin having an EEW of about 190 (theoretical value of n=0) has been found to consist about 88 percent of molecules in which n=0~ 10 percent of n=l and 2 percent of n=2~ Similarly, a typical higher molecular weight DGEBA resin, such as is used in some solution coatings and having an EEW of about 540 (theoretical value of n=2) ~: was found to have the following composi~ions: >50 percent of n = 3-5; about 15 percent of n - 2; 15 percent of n = 1, and 20 percent of n = 4.
~- Exemplary bisphenols from which El epoxides i~ 15 of the general formula (a) given earlier herein may be ;; ~
. prepared, are as follows:
., OH OH OH
mononuclear I 1 1 OH
. dihydric ~ ~ ~ ~
.s.~ phenols ~ ~ Q `OH ~
s~ H
~; OH OH OH

CH3~0 :

.~, , ~18,224B-F -20-,' ~ ,~, f ~

L3~

:! bl~phenOl~ ~O_~CH2 - C} OH Bisphenol-F

,~ H ~ ,H3 ~ OH Bisphenol-A

,.~ ~1 cl ~~ ~ CCH3 ~ OH ~isphenol-A

HO ~ CH ~ OEI Tetrabromo-; , Bisphenol-~
Br CH3 Br Additional exemplary bisphQnols will be found in Tables I and II: The Chemistry of_Phenolic Resins;
R. W. Martin; pp. 6~-79, Wiley & Sons; ~.Y~, N.~., (1956).
El epoxides of the type represented by formula (q) may readily be prepared by "capping" corresponding $ ~ 10 apoxides of formula (a), with one or more phenols R~ ~ OH, R , r and R20 being as defined eaxlier ~;- herein, in a manner familiar to those skilled in the poxy resin art. It has been found that the wetting ability of the resin can be varied in this manner to ensure better wetting on a given type of substrate.
It will of course be recognized that formula r: (q) will only be representative o~ the capped product ;~ as an "average" structure. That is, even if the phenol ' and type (a) epoxide are reacted in equimolar proportions some of the product molecules will not be capped and others will have had both oxiranes reacted out. The :' ,~ 18,224B~ 21-.~, ~
,, . .. ~ .
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3~3 epoxide and the phenol can be r~acted in other than 1 to 1 ratio, so long as the Eh~ of the product i~ not raised a~ove 5500.
Suitable E epoxides for the practice of the present invention are vicinal epoxides, other than those of the preceding formuias (a) and (q), which have EEW's within the range of from 90 to 2000 and are con-vertible to water-dispersible products by reaction with orthophosphoric acid, followed by neutxalization with a base. Those skilled in the art, with the guidance . afforded by these specifications, will be readily able to determine whether the latter criterion is met by any . given candidate epoxide.
.:j Representative kinds of E2 epoxides are mono-~: 15 to penta-unctional epoxides of types.~b) through (p), following:
(b1 a methylol- or alkoxymethyl-substituted : .
phenylglydicyl ether of the following ~ormula:
`$ ;:~ O
O-CH2~ H2)a ~, (YOCH2 )~R

.,x, P
wherein Y is H or a Cl to C4 alkyl or alkenyl ~ group, .~ ~ each YO-CH2- group is either ortho or para ....
~` to a glycidyloxy group, . : x i.s 1, 2 or 3, p is 0 or 1 a~d a is l or 2, Rl, independently in each occurrence~ is H
.~ methyl or ethyl, , ' ~:
18,224B-F -2~-.
~, .3 ::

R is a Cl-C12 alkyl~ alkenyl~ cycloalkyl, phenyl) alkylphenylJ phenalkyl, phenoxy, -Br~ -Cl group or a CH -C-~H
T ~ 2 ~1 2 ~6 (C~I20Y)y , ,.
wherein y is 0, 1 or. 2 Y and R are as above de~ined, , T is a Cl-C4 alkylene or alkenylene group, ~C(CF3)2~ -SO2-~ ~S~J ~O~ or a valence bond, ;, ~ R is -Br, -Cl or a Cl-C12 alkylJ alkenyl, ,~ 10 cycloalkylJ phenylJ alkylphenyl, phenalkyl or phenoxy group, and t is 0 or 1;
with the proviso that (x + a) cannot exceed

4 and (x + y) is from 2 to 4;
~c) a methylol- or alkoxymethyl-substituted, ~2,3-epoxy)propylbenzene of the ~ormula:
CH20Y')b 7) ~ ~ CH2-C/-~H2 ; wherein:
b is 1 to 3, d is 0 or 1, ~ R7 is C1_C12 al~yl or -CH2 CLCH2 J
,;~ 20 Y' is ~ or a Cl to C4 alkyl or alkenyl group, .~ Rl is H, methyl or ethyl, - wil:h the proviso that (b ~ d) cannot exceed 3;
(d) di and trioxides o~ acyclic or cyclic, C4 't, ;', to C28 hydrocarbons or esters containing . ~
18, 224~3-F -23-, 3~

t~o or three noll~romatic, carbon-to-carbon doubl.e bonds and, opti.onally, a -Br, -Cl or ~F or hydro~y substituent, ~ (e) epoxy ethers of ~le :formula R -O-R , wherein .~ 5 each of R8 and R9 is the same or a different monovalent radlcal derivab~e by abstraction of hydrogen from a C3-C12 aliphatic-, alicyclic-or phenalkylene-oxide;
(f) 2,3-epoxypropyl halides, alcohols or esters ~ 10 of the formula: R,l ,i~;- H2~dC-CH2-A
wherein A is -Cl, -Br, -OH or -O-C-R , R is -H, -CH3 or -C2H5 and R2 is a Cl-C15 hydro-~ carbyl group;
'~f' 15 (g) glycol monoethers o~ the formula~

CH2 ,CHlO~g0~CH2~c~cH2 and glycol ~ diethers of the formula: ~ .

,~ H2~-C-CH2--~O~cH2-c ~ C~2 ,1 2 ::~ R X R
wherein, R is -H, -CH3 or -C2H5, R10 is -~ or -C~3, X is -H, -CH3 or -C2E5, g is 19 2 or 3 and h is an integer of from 2 to 10;
h) diglycidyl ethers or esters of the formula:
f - ~2C C-CH2 o (c~ )i R _(Co)j-O-cH2-R-cH2 s.:~ wherein Rll is a di~alent hydrccarbon radical of from 2 to 20 carbons, R is -H, -CH3 or -C2H5 and i and j independently are 0 or 1;

18,224B-F ~4~

~ t ` ' ~ , ~ ' '. .
' ' r,~

. (i) mono o~ diglycidyl eth~r3 of ~O-c~ CH20H and ~O~O~OH

,, j) mono-~ di or triglycidyl ethers of glycerine;
(k) trifunctional aromal:ic epoxides : ; R~

S ~ ~Z [Z ~j C R13 .' : H2 C,~ H2 3 OR 4 oR14 Z-CH2~ R15 ~L
C~2-z a~d ~; z Z

:~ ~ ; wherein Z is ~2C-C-CH2-O-, ., . ~ .
~, Cl C2 alkoxy, Cl-C6 alkyl or C2-C6 '` - alkenyl7 R13 is H, Cl-C12 alkyl or C2 C12 y ~14 is a Cl-C8 alkyl, alkenyl, cycloalkyl, cycloalkenyl or aralkyl group, ortho or para ~: -~i to those Z-CH2- moieties on tha benzene ring ~:
.~ to which said group is attached, ~1 is as previously defined and R15 is a Cl-C~ alkylene or alkenylene grou~ or -S0 18,224B-F -25-D , -.` ''. .
~: . .. .
.
. : ~ : : . . . . . :

.~ . .

L3~3 ":
'' (1) tetraglycidyl ethers o~ the formula:
, 2 ~R16 ~ Z2 wherein R16 is a Cl to C69 diva.lent aliphatic hydrocarbon ~ radical, .". O
~ 5 -C-, ,C(CF3)2, -SO.2-, -S-, -O- or a ~alence '',`~, ' O
~; bond and Z is -O-CH2-C-CH2;
:. R
(m) tri- to pentafunctional epoxy novolaks of the formula:

17 ~ R18 ~ , wherein p is 1 to 3, ! ~ : R17 is H or -CH3, independently in each .` occurrence, R18 is an alkylene group of 1 to * ca~bons and Z is -O-CH2-C-CH2;
Rl (n) methylol substituted, oligomeric monoepoxides o~ the formula:
,, ~ . ~4.

HOCH2 ~ H20 ~H2-CH-CH-O 1 OH
r J ~2C~ ~ CH~-( -CH2-C~-CH~-O
~ ~ ~19 L ~ J ~l01~2c ~C~I OEI

~: 18,224B-F -26-,j .

;, ~. \ ' ' ' .
~, :
: ~

,: ~ ~: ,. . :

3~'13 wherein u i~ 0, 1, 2 or 3, .R , .independently in each occurrence J i~ H, miethyl or ethyl and R19g independently in each occurrence, is a Cl-C12 alkyl, alkenyl, cyc.loalkyl, phenyl~ phenalkyl or alkylphenyl grou]?;
~o) epoxiaized triglycerides of unsaturated ~atty acids of up to 18 carbons each; and s (p) one to one adducts of substituted phenols with ~ 10 diglycidyl ethers of substituted bis-phenol~, !: o:E the forlmlla:
Rp Rr Rr (~O-CH2 ~ CE2 -o--~--R _~ 2 , 1 2 ~ CH20Y)~ ( H20Y~W (C~20Y)w R
..." ~
i wherein R , R , R3 and r are as de~ined in, . .
- ~: preceding formula (a), Y, RS and p are as `~` 15 above defined in formula (b~, v is 1, 2 or 3 . ~ and w, independently in each occurrence, is ~` 0~ 1 or 2.
; `
E~emplary, speci~ic E epoxides of types (d) through (m), and (o~. are as follows:
. 20 TYpe Epoxide (d) Butadiene diepoxide, limonene dioxide,linalool ~: ~ dioxide, 4-vinylcyclohexene dioxide and trivinyl-~;~ benzene trioxide. (See also Example 13.~
(e~ Di~lycidyl ether, 4,4'-divinyldiphenylether dioxide, bis(2~3-epoxycyclopentyl)ether and :~
the glycidyl ether of 3~4-epoxy-1-butanol.

~,: .
i . 18,224B-F -~7~
,:. :, :
: ' !

~ :

Continued Type Epoxide (f) Glycidol~ epibromohydrin, 2-methyl epichloro-hydrin, glycidyl ben;zoate and glycidyl methacrylate.
(g) The monoglycidyl ether of ethylene glycol and the bis(2-methylglyc:idyl)ether of tripropylene glycol .
(h) Ethylene glycol diglycidyl etherJ 2-butene--1,4-diol, diglycidy:L ether; and the bis(2--~thylglycidyl)ether of 1J l-dimethylol-3--cyclohexene.
(i) 2-glycidyloxymethyl-5-hydroxymethyl-t~trahydro-furan and the bis(2-methylylycidyl)ether of ~5 2,6-dioxane diol.
OH ~O
(j) HO-CH2-C-CH2-O-CH2-C - CH~ and J~)\
HO-CH--~CH2-0-CH2-C CH2)2 . H
(k) 1,3,5-tris(glycidyloxy)benzene, 2,6-diglycidyl-phenyl glycidyl ether, tris(4-glycidyloxyphenyl) methane, 2,2',4'-tris(2-methylglycidyloxy)di-~- phenyl, and H2C-CH-C~I2-1:~-CH2~ CH2-0-CH2-CH-CH2 O CH3 ~ -CH2 ~ OCH3 2C CH-cH2-o-CH2 : (1) 2,2',4,4'-tetrakis(glycidyloxy~diphenylmethane.
~` (m) H ~ CH ~ CH ~ CH

~ , CH3 CH3 CH3 0 C~3 0 :~' CH2 CH2 CH2 CH2 CH2 ~H o~ CIH O~ CIH o_ CH
' CH,2 CH2 CH2 ' CH2 ~ CH2 ::

~18,;224B-F -~8-.~ ~
...

'. ~ ~ ' , . ' ' (The penta-glyciclyl eth~r o~ the condensation product of 5 molecules of phenol with 4 mole-cules of acetone.) (o) Epoxlde molecules of this type constitute the reac~ive componen~s of epoxidized Soybean - Oil. A commercial version of this matPrial (FLEXOL~-EPO; Union Carbide corp.) is an : epoxidized mixture of triglycerides of C14 to C18 fatty acids. The proportions of satur-ated and unsaturated acids in the oil (prior o epoxldation) axe as follows:
Fatty Acid Formula Wt. % # o~ C=C
Myristic C14H~802 .1 0 Palmltic C16H32O2 8. 0 0 Stearic C18~362 4- 0 Arachidic ~20H402 ~ ~ O

~- Myristoleic C14H~602 .1 Palmitoleic ~16~302 O 2 Oleic C18H342 28~ 0 Linoleic C18H32O2 54. 0 Linolenic C18H302 5 ~ 3 :

~:- The theoretical EEW for epoxidation of all double bonds in the oil is 210.

,i, ~
~:: Types (b), (c), (d)~ (g), (m), (n), (o) and (p) are preferred among the above listed kinds of E2 epoxides. Within the latter group, types (b), (c~, (n~
.~` and (p) are particularly preferred by reason of contain-~` ing methylol or loweralkoxymethyl substituents which ~:
: render rapid].y heat-converting those El/E2/H3PO4 product 30 . mix~ures comprising thsmO
:, , ~
~ 18~224B-F 1 -2~ ; ~

.
~ ~ . . . ; , t~ 3 .,~

Epoxides of types (d), (g), and (o) have been shown to improve film formation, dxied film adherence and/or cured film flexibility. An epoxide of type (m) has been shown to improve film formation, cured film adhesion and sol~ent resistance (but to reduce cured film flexibility).
Most preferred E2 epoxides are those of formula (b) in which Y is H or -CH3, x - z, p = 1, and R is an aliphatic hydrocarbyl group of 1 to 12 carbons~
Exemplary epoxides of formula (b) which can . be employed in the process of the invention are those ;~ methylol-substituted glycidyloxybenzene compoun~s deriv-able from the following known methylol-substituted phenols and bisphenols by known methods (see, for example~ U.S.P~
39859J255; columns 5-7)~
OH
r H 2 ~ CH2H Q = Bx, methyl, ethyl, propyl~
isopropyl, n-butyl, t~butyl or nonyl;

Q
:~: OH OH OH
C~ C~ 2}~ 2~CH20 CH ~ CH3 HOH ~ CH C~2H
~O ~ CE~ ~ _OH ~ H ~ C ~ OH
CH2H CH20H HOH2C 3 CH~OH

,::

18,224B-~ 30 .,:. .
.

,~ .;, . . .
,.

3~i~3 HO}I2C CH2H EIOH2C CH2~
HO ~ O ~ and ~ CH ~ OH

~IOH2C HOH2C CE~ CEI20H

A specific, methylol-substituted, mononuclear :~ diepoxide (of formula (b)), disclosed in U~S.P. 3,925,315 is ~OH~C ~ O-CH2-CH-CH2 .

H2~, YC-H C-O
,: ' Specific dinuclear type (b) diepoxides are :~ the following "APOCEN~" resins, available from Schaefer Chemicals, Inc., P. O. Box 132, Rivertone, ~ew Jersey:

L ~

cn2 - C}i-CH2-o~)2 ( 3~2 and C~I2/\~CH_CH2_~CH3~_C~2_CH/_\

`: HOH2C 3 -~

Mixed glyci~yl ethers of mono-, di- and tri-methylol phenol can be prepared by "epo~idation" of the correspond ng mixture of allyl ethers, which is marketed ~. 15 as MæTHyLo~ Resin 75108 by General Electric Company.
: (See U.S.P. 2,965~607 for an epoxidation procedure.) ,' 18,224B-F -31-,~

:

:.. .

These mixed ethers are representati~e of type (b) mononuclear, monoepoxides substituted with from 1 to 3 methylol groups.
Exemplary E epoxides of foregoing formula (c) are:
~ H2H
HOH2C ~ /~ and /~

H0~2C ~ OCH3 :`
which can be made by the "epoxidation" procedure of Example XII, UOS~P~ 2,965,607, from the xespective pre-; 10 cursor compounds, 1-al~yl-2,4,6-trimethylolbenzene ~U.S.P. 3,906,126) and 1-allyl-2-methoxy-3~5-dimethylol-benzene (U.S.P. 2,707,715).
Some or all of the methylol groups present in epox~propyl benzene compounds of the preceding types, ~ 15 or in the glycidyl ethers ~eri~able from any of the : foregoing methylo~-substituted phenols, can be conver-`~ ted to corrasponding alkoxymethyl groups by well known methods commonly utilized in making benzyl ethers. ~ -Epoxides of formula ~n) may be regarded as oligomers of methylol-substituted phenyl glycidyl ethers.
They may be prepared simpl~ by heating the latter ethexs .: ~
.
: 18,224B-F 3~~ ;.

~ 3 to a temperature (such as about 165C) at which the methylol groups interact with -the oxirane groups at a reasonable rate and maintaining that temperature ;~ until the EEW of the resi~ has increased to a value commensurate with the desired value of u~
The specific oligomer in which (in formula (n)) the average value of u is about 105~ Rl iS H and R 9 is t-butyl, has an EEW of about 940 and is obtain-sd by heating tha corresponding monomer ~or a~out 2.3 hours at 165C.
,~: Some or all of the residual methylol yroups in such oligomers of course can be converted~ by known ~ methods, to alko~ymethyl groups to provide a variant : type of E epoxide.
. 15 Exemplary epoxides of fo~mula (p) are:

,~ , ~ H20H
:i ~ r----~ QH r----~ H ,----~ O
CgHl ~ H ~ H

CH2~
and , (CH3~3C~O C~2_1_CH2_0 ~--C~ H 2 ~ 20H 3 .~ 18,224B-F -33-, . .

. .
~' .~' ' :,:

~3~

which can be prepared by reaction of the corresponding 4-alkyl-2,6-dimethylolphenols and diglycidyl ethers of Bis-A-type diphenols in the presence of a catalyst, such as ethyl, triphenyl phosphonium acetate, in a known manner.
,-:
~ The practice of the ,present invention is not ,~ restricted to the use of one species of E2 epo~ide at a time or to such epoxides in ~which all Y, Rl, R2, R3, R6, Z (etc.) groups are th~ same throughout the molecule.
, 10 Two or more distinct E2 epoxides of any or all of pre-ceding form~las (b) through (p) may be combined in a single reaction product with phosphoric a~id. A given epoxide may comprise as many different kinds of the specified substituent groups as it is synthetically feasible to incorporate in individua~ molecules of the latter formulas.
When the mixtures of the present invention are to be made by co-reaction of a phosphoric acid source ~ material with an El and an E epoxide~ the reaction may ';'~ be carried out in either of two ways. The El and E2 epoæides may be mixed and then contacted with thè acid~
or first one and then the other of the two types of epoxides may be "reacted in". It might be expected that the second mode of practice would result in the , 25 presence in the final product of molecules consisting l and E2 residues joined by phosphodiester groups.
,:, ~`' However, this generally will only be the case i~ water is essentially excluded from the mixture and~any free acid remalning after the first reaction has been removed , ,18,224B-F -34-.' P~ .
~ ' .
:, :

before the sPcond epoxide i5 added. Further~ any such diester gxoups will tend to undergo hydrolyais whenever the product is contacted with water.
In general, it has b,een found preferable to react the acid with the El and E2 epoxides sequentially.
When this is done, different reaction temperatures may be employed ~or the successive conversions of the two types of epoxides. A~ a rule, the E2 epoxide will be the more reactive of the two and is best introduced after the E epoxide has been at least partly converted.
~ Phosphoric acid source materials which may be ;~ employed in the practice of the present invention include 100 percent orthophosphoric acid, the semi-hydrate 2H3P04 H20 and aqueous solutions containing at least 18 weight percent H3PO~ (~ 1 mole H3PO4 per 25 moles of water). The various condensed forms (polymeric, partial anhydrides) of phosphoric acid~ - pyrophosphoric acid .
and triphosphoric acid may also be used.
When the acid source material is of the con-densed type~ sufficient water should be supplied, at some stage prior to curing the resinous end-product, to ensure that no substantial proportion of P-O-P
links are left in the cured resin~
Ordinarily, aqueous ~hosphoric acid solutions, ~-~ 25 particularly 70-90 percent solutions J will be preferred.
When a condensed form of phosphoric acid is utilized as the source material, the stage in the process at which .~ .
P-O-P hydrolysis is e~fected will depend on whether or not minimization of water content during the reaction 18~224B-F ~35~

~3~

~- ls desired. If a condensed .source material is to be fully utilized as H3PO~ in the reaction, sufficient time should be allowed for complete P-O-P hydrolysis to occur.
i. 5 The rate at which the oxirane groups are converted in the El/H3P04 reaction and the makeup of the products obtained are of course dependent on such ; parameters as water to acid ratio~ acid to oxixane ratio, solvent nature, temperature and contact time.
It has been found that the reaction generally . involves more than just adduction of P-OH with oxirane !,~ groups. Unless pains are taken to ensure the absence of water in the reaction mixture, the product will generally include substantial proportions of molecules . 15 in which at least one oxirane group has been converted to an alpha~ beta-dihydroxy group, i.e. J a "glycol"
. group. This apparently results not only from H -cata- s .~ lyzed adduction of water with oxiranes but also from phosphodiester group hydrolysis. As a consequence of 20 the former reactiong some free phosphoric acid will a generally be present in the reaction product, even ~::. when the amount of acid used is such as to provide substantially less than one P-OH per oxirane group. ~
; It is apparent that the presence of water ,¦
has a more profound effect on the composition of , epoxide/H3P04 reaction products than has hereto~ore been realized s~ Introduction of water to the reaction mixture . may be avoided by use of 100 percent phosphoric acid 18,224B-F -36- ¦
:~` t !~

':~ t ,:

~ 3 as the sole acid source material. However, it has been found that esterification of the secondary alco-holic hydroxyl groups in DGEBA type epo~ides tends to occur to a minor ~xtent. Since water is also produced by this reaction, steps must be taken to scavenge or remove any evolved water if attainment of really low glycol to ester group ratios in the product is desired.
This is most readily done by employing some P-O-P
group-containing acid source material (such as pyro-phosphoric acid or polyphosphoric acid) with the 100 percent acid. Esterification of alcoholic hydroxyls (and water production) is also minimized by carrying out the reaction at relatively low temperatures (such `~ as 60-80C).
; 15 If desired, a suitable P-O-P group-containing aci~ source material for the latter purpose can be made simply by in-situ, pre-reaction of pyrophosphoric acid with less than the amount of water required to react out all of the P-O-P groups.
~; 20 ~lthough the presence of (sali~ied) phospho-monoester groups is essential to water-thinnability of the El/H3PO4 reaction product, it is not necessary that ~- a high proportion of the oxirane groups in El report in the product as ~ster groups, rather than as glycol groups. On khe contraryJ "esterification" products of DE~-667 in which the number ratio o~ glycol to ester groups is as high as 18.3 to 1 have been found to be water-thinnable and to yield use~ul coatings when c~red (See Example 11 herein.) The foregoing finding constitutes "
"' ~18,224B-F ~37-`~:
, ~ ` ., - , - . ~

a most unexpected and surprising discovery and has important cons~quenc~s to the ~uitability of the compo-sitions of the present invention as linings for food containers. One consequence is that the phosphoric acid ~and the salifying base) can be usPd in such minor amounts ~as lit-tle as 0.75 grams of H3PO4 per hundred grams of DER~-667~ for example) that the cost of the final product is substantially less than it would other-wise be. Another consequence is that when a ~ugitive base is employed~ the amount o~ the base evolved prior to (or during) curing is so small that the problem of recovery is correspondingly reduced. A further, very important consequence is that the amount of the (fugitive) ba~e retained in the cured coatings is essentially nil (within the range cf from 50 parts per billion down to undetectable amounts).
The amount of water provided to the acid epoæide reaction can vary from O to 25 molecules per molecule of H3PO4 provided by the acid source material. Amounts of water in excess of about 2-4 moles per mole of the acid will generally result in an inhomogeneous reaction mixtuxe unless a good solvent for water is included therein. The presence of water in relatively high pro-, , .
portions does not necessarily result in as low phospho-ester to glycol group ratios in the reaction product as might be expected. Ester to glycol ratios as high as 1 to 2.3 have been obtained (using DER~-667 as the epoxide and acetone as the reaction medium) at watèr to acid mole ratios in the vicinity of 25 to 1 ' 18,224B-F -38-.

~'~ ' : , ' , , ~3~ 3 The product resins will generally be water--thinned and it is usually preferable to have water presen~ in the mixture before the solvent is removed.
Accordingly) the presence of relatively large amounts of water during the reaction does not pose any large problem on these accounts. It has been found that prolonged reaction times are essential to attainment of high oxirane conversions at higher water concentra-tions. However, it is highly advantageous to process economics to be able to recycle recovered solvents having substantial water contents. Accordingly, the optimum water content for the reaction o any particular El epoxide will need to be determined. This will not require undue experimentation and methods for doing it will be made readily apparent by the examples herein.
~; The amount of acid introduced to the reaction !~' .
by the acid source material should be such as to provide ` about 0.3 or more acid hydroxyls (hydroxyl groups attachedto phosphorous) per oxirane group present in the El epoxide reactant. Preferably, however, the amount of acid is kept bel~w 1/3 mole of H3P04 per equivalent weig~t of El (i.e., below 1 acidic hydroxyl per oxirane), thereby avoiding substantial decreases in water-resis-tance of the cured products. When E is DER~-667 (or an equivalent DGEBA-type epoxide), it is highly pre-~-~ ferred that not more than 1 part by weight of H3PO4 be provided per 100 parts of El.

' ~ .
~ 18,224B-F -39-.~, . .

. . . ~
~ . . . . .

Greater amounts o acid, up to the point where the reaction mixture becomes undesirably non--homogeneous, may be employed. However, the use of more than enough H3P04 to provide about 4 acidic hy-droxyls per oxirane may result in the inclusion of enough free phosphate salt to have an undesirable effect on the properties of th,e uncured or cured product resin, thus necessitating removal of at least part of the excess acid - preferably before a base is introducedr The epoxide/acid reaction can be carried out neat and a reaction medium (solvent) is not nec-essarily required. However, as discussed earlier herein, the use of a medium is essential to homogeneity of the reaction mixture when the amounts of water and/or ~I3P04 present are high relative to the amount of the-epoxide.
Better results are obtained when the reaction mixture is homogeneous and it is generally preferable to employ a reaction medium in any case.
Suitable media for the reaction of the present process are inert materials which, in admixture with the reactants, form a solution or disp~rsion which is fluid at the reaction temperature to be employed. As employed in the present application, the term "inert"
mean~ that the medium does not detrimentally react with any material present to such an extent that at ~ .
least one of the objects of the present invention cannot be realized.

18,224B-F ~40-~ .

: .
_e.,._ ,~ :~ . : : :
-; . . .

3~

Preferred media are inert organic compounds or mixtures which are liquid a~ ordinary temperature~, have boiling points ~elow 150C and are solvents for the epoxides and phosphoric acid source material(s) to be used. The sol~ent should also be able to dissolve enough water to ensure that tha desired ratio of dis-solved water to acid (or oxirane groups) is attained.
Exemplary of such media are dioxaneJ glycol ethers, lower alkyl acetatesJ methyl ethyl ketone, acetone, ethanol, isopropanol and methylene chloride in admix-ture with any of the preceding solvents. (The latter alcohols exempliy "inert" solvents which are not detrimentally reactive to an intolerable extent~ They are particularly useful (as co-solvents) when precipi-~5 tation tends to occur in their absence, as w~en aqueous .. . .
H3P04 is added to a dilute solution of an EL resin in a medium comprised solely of dichloromethane~) The nature of the reaction medi~n effects both reaction rates and product composition. As a general rule, the rate of oxirane conversion by P-OH
~` adduction and the proportion of diester groups in the reaction mixture is higher when a poor solvent for water - is employed as the reaction medium.
At a temperature of abou~ 60C, the poor (or non-) solvents for water faYor formation of higher pol~ner chains made up of E epoxide residues linXed together by diester groups:

18,224B-F -41-' ~ I

H O H
- C -- CH2 ~ O - P - O -- CEI2 -- C -OH OH

Thus~ if DER~-667 is reacted with 1 percent of its weight of H3PO4 (as 85 percent aqueous H3PO~) in 100 percent CH2C12 at 60C, the reaction mixture yels in about 4 hours. The chemical activity of water in a solvent such as dichlorome~hane~ under these conditions, does not appear to be high enough to result in substan-tial hydrolysis of oxirane or ester groups. (However, the latter type of gel could be dissolved in a more water-miscible solvent and hydrolyzed to a fully useful product containing about equal numbers of glycol and ;~ monoester groups.~
If the reaction medium also contains as much -~ as 25 weight percent of a CH2C12-miscible solvent for water, such as acetoneJ diester formation is still the predominant reaction (at ~0C) but the product is not a gel. At a temperature of 115-120C) the activity of the water (contained with the H3PO4) in a medium con-sisting of 75 weight percent CH2C12 and 25 weight per-cent acetone, is substantial. Diester formatio~ does not proceea as ~ar and hydrolysis of all of those diester groups which are formed occurs. As the pro-portion of acetone is further increased~ howeverg diester formation drops and the monoester content in the final pr~duct increases. Direct adduction o~ water 18,224B-F -42-:
~ .

- :: - . -.
, ~ . -.~ .. ..

with oxirane groups apparently is the predominant reaction (at 115-120C), but the ratio of glycol to monoester groups goes down as the proportion of ace-~
tons in the C~2C12/acetone mixture increases.
The nature of the medium in which the neutral-ized reaction product is formed is also important.
That is, the medium which serves best for the prepara-tion of a given reaction product is not necessarily the medium from which the most stable or highest solids content dispersion of the neutralized product in water can be obtained.
Thus, tests have shown that although higher monoester contents are o~tained from the (above dis-cussed) reactions of DER~-667 with 85 percent H3PO4 in acetone alone than in acetone/CH2Cl~ solutions, ths presence of a minor amount of the dichloromethane is helpful to dispersibility of the neutralized product formed when water is added and the organic medium is removed. It has also been founa thatg in general, ~; 20 product particles form~d upon stripping the neutralized epoxide/acid reaction mixtures exhibit less te~dency to ~I agglomerate when derived from solutions in dioxane or -~ methyl ethyl ketone - particularly the latter solventO
~ Accordingly these solvents may be employed to parti-;~ 25 cular advantage as media for the preparation of those neutralized acid/epoxide products which are inherently more difficuLt to disperse in water.
; If extractive removal of excess phosphoric ~- acid at any stage prior to neutralization is contemplated~

~-~ 18,224B-F ~~3~
- '~

:: ''' ''~' ,~, -," ~
, it i8 of course feasible to include ~n appropriate amount of a so]vent which is not miscible with water, or prone to emulsify therewith, in the reactlon medium.
Also, solvents which are base sensitive, such as acetone, should first be removed if morle than the stoichiometric require~ent of base will be employed to effect neutrali-zation.
Mixtures of two or more solvents are in some instances preferred as providing a medium having a desired combination of solvent action and initial or ~- azeotropic boilin~ point (reflux temperature).
Suitable reaction temperatures range from the lowest temperature at which P-OH adduction with oxirane groups (in the El epoxide) proceeds at a useful rate to temperatures so elevated that (1) detrimental reac-~ tions (as between an alcohol reaction medium and the ,;~ phosphoric acid) occur to an intolerable extent; or (2) excessively high solvent vapor pressures are devel-oped. Temperatures wi~hin the range of from 50C to 150C will generally be found satisfactory but it is preferre~ to maintain the reaction temperature within ' the ranye of from 70C to 135C The ranye of from 100 to 125 D iS particularly preferred and a range of 110-120 appears to approximate the optimum for commer-cial practice of the present process invention.
The nature of the interdependence of tempera-, .
ture and solvent effects has been indicated in the preceding discussion herein of reaction media.
, .

18,224B-F -44--' .__ __ , Pressure is an important parameter of tha reaction only in ~hat operation under elevated pressures -at least equal to the au~ogenous pressure of the reaction mixture - are required when reaction temperatures above the normal atmospheric boiling point of the reaction medium are empioyed. The reaction can of course be carri~d out at sub~atmospheric pressures if desired.
Contact time is an important parametex of the present process only in ~hat the reaction is generally allowed to proceed until less than l percent, and pre-ferably less than 0.5 percent of the oxirane groups originally present are consumed. It is only necessary to con~ert as much o~ the epoxide as is required to produce a reaction product having essentially the char-.: .
acter of the more highly reacted epoxids/acid products of the invention. That is~ epoxide conversion need be -; only essentially complete.
In ac~ordance with well known principles, the rates of the several reactions which tend to occur will be higher at more elevated reactio~ temperatures and shorter contact times will be required at such temperatures.
As a general rule, prolonged contact will tend to result in a higher degree of diester hydrolysis.
In most instances, contact times of from about 1 hours (at temperatures in the vicinity o~ 150C) to about 24 hours (at 60--70C) will be satisfactory.
Ordinarily, essentially complete conver~ion of ~he E
, .

18,224B-F -45-~ 3 ~ A~ a~

epoxide to a product whieh will be a water-thinnableJ
when neutralized, can be attained in 3-6 hours contact time at a tem2erature of l~S-100C.
Procedure

- 5 The reactions of the epoxides with ~he ortho-phosphoric acid source materials (and such water as may be present) are readily carried out in conventional eguipment.
The first step will normally consist of dissolv-ing the epoxide or epoxides in the reaction medium (or in the component thereof which is the best solvent for `~ the epoxide). In the case of the higher molecular weighk (El) epoxides, at least, dissolution in most solvents is somewhat slow at ordinary temperatures and will usually requirQ agitation of the resin/solvent mixture for a ; period of time such as 8 hours or more.
The acid source material, usually 85 percent aqueous H3P04, may be pre-dissolved in or diluted with one or more components of the reaction medium, to facili-tate mixing with the epoxide solution. In any case~ it will usually~be more convonient to run the acid material into the epoxide solutionJ rather than vice versa. In-tsoduction of the reactants to each other gradually and/or at low temperatures is not necessary unle~s a highly reactive epoxide (more often the E2 epoxide~ is ` employed in 1:he reaction. (An example of a highly reac-tlve E epox~ide is the diglycidyl ether o bis-phenol-A.) ~` In the latter circumstance, it is desirable to operate initially at as low a temperature as will ~ ' - 18,224B-F -46-;~`

permit the reAction to proceed at a satisfactory rate.
In this manner (and by dilution)~ reactions leading to gelling can be minimized. Thus, in simultanaous or sequential reactionsJ the reactants may be inter-mixed as thoroughly as possible, prior to onset of a given reaction~ by pre-chilling, mixing and stirring the reactants (and medium) at a l~w temperature (~5C, for example) for a period of up to a day or more. After this is done, the mixture should be allowed to warm slowly, to avoid any tendency for a sudden exotherm to occur. After the more reactive epoxides have been largely ; converted, iDe... after the oxirane content has decreased sufficiently, the mi~ture may be taken to a higher temp-erature, to drive the reaction(s) to completion more rapidly. However~ temperatures substantially in excess of about 150C generally axe to be avoided, during the reaction and also subsequently, as during so~vent removal.
; ~ Ordinarily, the mixed reactants are heated, ;
preferably with agitation, to the desired reaction temp-` 20 erature in a vessel suitably equipped with a ref~lw~ con-i~ denser, a pressure seaL or such other apparatus as is appropriate. The vessel contents are kept at temperature at least until sufficient oxirane conversion has been attained to result in a water-thinnable product (upon base additionl.
Th,e r0action mixture is c:ooled and then ~ ~ "neutralized" as discuGsed belowg diluted with water ; ~ and stripped of lower boiling materials. If a reaction .. . .

18,224B-F ~47~

" ~
,, .

; , "i ~ ' ' ' medium consisting of or comprising a solvent higher bolling than water has been used for the r~action, addition of water may be delayed until the high boil-ing solvent~s) have been replaced with a lower boiling solvent (which is then stripped off after the water is added).
It is generally d~sirable to add the water gradually, with good agitation3 as otherwise coagula-~ion of the salified (neutralized) resin may result.
Base ~eutralization The reaction product of E3P04, E and/or E
may be neutralized with any base of such nature that the neutralized product will be water-thinnable. De-pending on factors which will be apparent to those skilled in the art, complete neutralization is not nec-essarily required in all cases. That is, the acid/
epoxide reaction product need be reacted with only as much base as is necessary to provide the proportion o~
salified ester P-OH groups required to ach.ieve water--~ 20 -thinnability. ~Iowever, provision of at least one equivalent of base per ph~sphate ester group is gener-~- ally preferable and will usually be essential when the acid number of the product resin is relatively l~w. At the other extreme, enough base may be provided to completely neutralize all acidic hydrogens present in the acid/epoxide reaction product (including any free H3P04).
Exemplary types of bases suitable for the practice of the present invention are:

18,224B-F -48-,,~' .
, . .
~' .

. : .
, ~ . . , :
.. . .

A. Alkali metal hydroxides, such a~ lithium, ` sod.ium and pOtassiUm hydroxides, etc.
`j These bases may be employed with re~ins ; which are to be used (as surface active materials~ for examI~le) in the forrn of the uncured salts or in which the reac-.. tive functions present (secondary alco-holic hydroxyls) may be utilized to l affect curing.
!i 10 Bo Oxides or hydroxides of alkaline earth ~' metals, such as beryllium or calcium, * . which form phosphates or acid phosphates having measurable water solubilities.
Again, curing of such salts will require the presence of the above-named reactive functions. ~he salts may also be util-, ~ ized as water-dispersible sealers or primers on materials such as unfired . ~ ceramics which are subsequently to be fired.
:' C. Oxides or hydroxides of other metals, such as copper and iron, which form phosphates or acid phosphates having measurable water solubilities, as such or as hydrates, complexes w.ith ammonia, etc.
D. Ammonia or ammonium hydroxide.
E. Or~anic bases. This class o~ bases ~: is highly preferred.and includes tha fo.ll~wing types of compounds:

~ 18,224B-F ~49~
,,,~
,~ , .,, ~ .

, . .
. :. - - ~.

~ 3 a. choline and guanidine;
b, aliphatic ~ono- and polyfunctional amine~, such as methyl amine, n--butyl amine, d:iethyl amine, tri-methyl amine~ d:iethylenetriami~e, n-hexylamine, ethylene diamine~
allyl amine, etc.;
cO cycloaliphatic c~inesg such as cyclo-hexyl amine, cycloheptyl amine, etc.;
d. aromatic amines, such as aniline, N,~-dimethyl anilinej diaminobenzenes, - etc.;
; e~ heterocyclic amines, such as ethyl-enimine, piperazine, morpholine, - 15 pyrrolidine, pyridine, hexamethylen-imi~e, etc.; and . alkanolamines and alkylalkanol amines, such as ethanolamine, dimethylamino-.. ~
ethanol, diethylaminoethanol, diiso-propanolamine, triisopropanolamine, 4-hydroxy-n-butylamine, 2-dimethyl-amino, 2-methyl, l-proæanol, etc.
Among each of the preceding classes a-~, those compounas which can be removed from the neutralized resin dispersions, during or after water boil-off, by heating to temperatures less than those re~uired to attain satis- ,;
~actory cure rates, are preferred. Particularly preferred are those organic bases of classes b and f which can be ... , j,.

~ 18,224B-F -50- ~

.' ` ~ ~ ' ' '' .-,:~,................................................................ . ..

removed by heating to ten~eratures below about 150Co ~his will generally ~e feasible with such bases having ~: boiling points o~ less than 150C at a pressure of 760 mm ~9.
Among the latter bas,es, the most preferred are amines of the formula ~R3, wherein each R is H, methyl or ethyl independently, except that not more than one R is H. In order of decreasing pre~erence, according to such factors as curing time (including the : 10 time required to effect de-neutralization and amine removal) and the viscosity and ease of strippinq of the neutralized reaction mixture, highly prefarrsd specific such amines are triethylamine, dimethylamineJ
trimethyl~mine and diethylamine. Triethylamine is par-: 15 ticularly preferred, not only with regard to the pre-ceding factors but also because such amounts of it as ~; remain in the cured coatings have been found not to .~ be readily leached out by water, even at such elevated temperatures as are encountered in processing of canned foods.
~ext most preferred are al~anolamines of the formula R'2N-CH2-CH2-OH, wherein one R' is H, methyl .~ or ethyl and the other, independentlyJ is H, ethyl or 2-hydroxyethyl. In order of decreasing preference, those specific alkanol amines which are more hi~hly preferred are ~,~-dimathylethanolamine, N-methylethan-~: olamine, ethanolamine and diethanolamine.

18,224B-F -51-::
. . .

:;~:

Trieth~nolamine is ~pparently not ~uitable for the neutr~lization of hiyher molecular weight acid/El epoxide reaction products of the invention.
DER~-667/H3P04 reaction mixtures neutralized with triethanolamine, di~uted with water and stripped (to ; a solids content of about 50 percent) have not yielded .i dispersions~ However, triethanolamine does not cause any problems when included wit:h CYMEL~ 303 (hexametho~y methyl melamine) in coating formulations of the disper-sions of the present invention~
It has also been observed that higher molecular weight El/acid products neutralized with dimethylamino-methylpropanolJ / N~CH3)2 (H3C)2C , disperse well . . CH20H
: 15 only if th~ amount of ~3P04 employed in the acid/epoxide reaction is greater than about 1 part per hundred parts of the resin (DER~-667)~
.' Mixtures of any of the foregoing amines and alkanolamines may of course be employed for particular applications where they are of advantageO Similarly, ~ separately prepared E and E reaction products with i~ H3P04 may be neutralized with different bases and then ~: combined, or may be combined first and neutralized with ...
:~ the same base material.
~eutralization is usually carried out by dilut-ing the acid/epoxide reaction mixture (including the . ~.- .
.:~ solvent used) with enough water to give a dispersion '~ ' 18,224B-F -5~-, ' . ` ~" ' ' . : ' . ' ' . ' which is satis~actorily easy to stir, and then adding the base (or vice v~rsa~. Wh~n no acid has been re-moved from the epoxide/acid reaction mixture, a very ~onvenient method is simply to add 2 equivalents of base (2 moles of an amine~ for example) for each mole of H3P04 (100 percent) charged to the reaction. How-ever, the amount of base required may be measured out according to a predetermined acid content in the material to be neutraliz~d. Alternatively, litmus or pH paper or a pH meter may be used to determine when to stop ; adding base. Another option which may ~e satisfactory in routine operation is simply to add the base, in in~rements and with good stirring, until the appearance or behavior of the stirring dispersion markedly alters in a way known to correspond to attainment of the desired degree of neutralization~ In general, however, a defi-nite pH, within the range of from 6 to 10, (preferably

6.5 to 9) will be preselected as the end-point for the nautralizationO Since the rate of the neutralization will drop off as the number of unneutralized, acidic ; hydroxyls present decreases, sufficient tIme should be allowed after each base addition to ensure that any apparent end-point is in fact a true end-point. Or-dinarily, no pH drift should be observable after about an hour.
Water-thinning and Utilization ffl the Neutralized H P0 ~epoxide Reaction Product 3~
Unless the neutralized product is to be used without being shipped, as little water as possible will .~
~ 18~224B-F -53-., .

~ .

. . _ _ . _ . . _ .
~.,~ ' ' . ' ~ 3~
.~
oxdinarily be used in prepariny it~ so tha~ shipping ; co~ts will be held do~n. However, prior to applica-tion to a substrate to be coated, the neutralized (and stripped) material will usually be thinned with additional water to a consistency dependent on the amount of additives or curing agents which must be co-dissolved, the mode of app]ication contemplated, the viscosity desired, the thickness of the coating to ~e formed, and so on. (It is generally preferred to prepare the aqueous product dispersions at a level ; of 50 percent solids and no difficulty has been experi-enced in further thinning such dispersions with water.) Energy re~uirements for water evaporation are of course another consideration. Ordinarily, the water employed as a thinner will be added at a relatively low rate, with good stirring, so as to avoid any tendency to form a quasi-stabla mixture of two discrete liqui~ phases.
~oweverg in some cases, reverse or even "all at once"
adaition may be permissible.
Stripping of the neutralized mixture is carried out in a generally conventional manner at a pressure appropriate to the normal boiling point of the solvent(s) to be removed. Care should be taken to avoid excessive kettle temperatures during stripping so that undesired hydrolysis of ester groups does occur. Undesirably high kettle temperatures are most likely to occur during the .
latter stages of stripping, particularly when a rela-tively high boiling, water miscible solvent has been 18,224B-F -54-,.

used in or as the reaction medium~ In the latter situation, a relatively low stripping rate or some other expedient, such as addition of a ~olvent which forms a lower boiling azeotrope with the water-miscible solvent, should be resorted to.
In an alternative mode of utilization7 the neutralized reaction product may be convertedJ as by spray-drying, for example, to a powder which can sub-~; sequently be dissolved in wat*r ox applied directly r 10 to substrates by known powder-coating techniques.
Aqueous solutions of the neutralized reaction ; products can be applied to various substrates ~o be coated, by such known techniques as spray coating, dip-ping, roller coating, brushing or by use of draw bars.
Removal of the water from the resultant aqueous films is readily accomplished by known methods, such as passing an air stream of controlled temperature and moisture ~ content over the film at a controlled rate, passing the ; film through a zone of reduced pressure, heating, etc.
~; 20 When the salt moities present in the neutralized reaction product (resin) are of such a nature as to be readily decomposed by heating and the base evolved upon decompo-sition is volatile, all or at least a substantial por-tion of the base may be removed during the water-removal operation.
Any base remaining after water removal ma~
be essentially removed by further heating, under ordin-ary or reduced pressure. Tha r~moved base ordinarily will be recovered, as by condensation or by acid scrubbing.

18,224B-F ~55~

. ~

t~

As indicat~d earlier herein, curing of the resin after water and base removal may be accomplished by means of any suitable agency. If an auxiliary chemical curing agent i9 to be employ~d, the agent may be introduced prior to water removal or subsequently (as by being sprayed as a solution in a volatile solvent on the uncured film). ln gensral, the most convenient and economical method of curing wil~ be simply by appli-cation of heat, as by baking, to effect cross-linking reactions between the reactive functional groups in the deneutralized coating, such as secondary hydroxyls, P-OH
groups and any groups reactive therewith, in added cur-ing agents, such as ureas~ melamines and phenolics.
Methoas_of Characterlzin~ Products lo Titration of Ac ds. The relative amounts of the phosphoric acid charged to the reaction which report in the product mixture as the free acid, as mono-ester groups and as diester groups may be determined as followsO A sufficient sample of the reaction mixture to proviae about 1 millequivalent (meq) of solids (based on acid present) is dissolved in 35 ml of a solvent consis-ting of 66.7 weight percent 2-butanone, 16.65 percent ~ , methanol and 16.65 percent water~ The solution is titrated with about 0.3N methanolic tetrabutylammonium hydroxide~
using a Metrohm/Herisan automatic titrimeter, to a second break (inflection) in the resulting conductivity versus - titrant-volume curve. 10 ml of water and 10 ml o 10 percent aqueous Ca~12 are added and allowed to react for .~, 18,224B-F -56-, .~

, .
',~`':~ : , , '3~i~3 about 10 minut~s, thereby converting all phosphomono-' . and diester groups to neutral calcium salt groups. The free phosphoric acid is converted to the monoacidic .. phosphate~ CaHPO40 All of the calcium-containing prod-ucts precipitate but ~ third hreak on the titration curve can now be observed~ without interference from :
the second monoester proton, upon neutralization of the . proton in the CaHP04 with more.of the quaternary hydrox-ide baseO The amount of base required to produce the first break is that consumed by the sole acidic proton in the diester and by the first protons in the monoester groups and the .ree acid. The additional amount of base required to reach the second break is that consumed by ;
.. the second (last) proton in the monoester groups and s 15 by the sacond proton in the free acid~ The additional ~ amount of base to reach the last braak is consumed solely ..:
by the last proton in the calcium salt derived from the free acid. If the total volumes of base solution required to reach the successive breaks are denoted as vl, v2 and , ~ 2~ V3, the relative amounts of phosphate present as mono-and diester groups and as the free acid may be calculated s~ from the following relationships:
r Free H3P04 = v3-v2 ,: ~onoester = 2v~ vl v3 y~ 25 Diester = 2vl-v2.
The proportion of the consumed epoxide groups reporting in the product as glycol groups (as a conse-~.
~ quence of hydrolysis reactions) is calculable rom the ~, , , 18J 224B-F ~57~
.

.
,,,~,~
,~
'~ ~

~,' ~ ' ' ' ~ ~3~3 ~ollowing relationship (assuminy the only conversion products are glycol, monoester or diester groups):

% eg = 100- MA (/~2(/~) ) (1 e -e o p wherein ep = equiv. epoxide presen-t in product as such (usually zero) e~ = equiv. of epoxidle charged to reaction eg = equiv. epoxide converted to glycol groups .
= moles H3PO4 charged to reaction ~m = mole % charged acid reporting as monoester %d = mole % chargea acid reporting as diesterO
: 20 Titration of Oxirane Groups. The standard method o~ analysis, using a 25 percent solution of tetra-methyl ammonium bromide in glacial HOAc and back-titrat-ing against crystal violet with O.lN solution of perchloric ~` acid in glacial AcOH, was found to be ~uitable and was employed in all determinations of oxirane contents given -~ in the following examples.
: 3. Viscosity Measurements. As an indicator of ~: ~O cross-linking and/or molecular weight changes, the vis-;:~ cosities of some of the reaction mixtures described in ~he Examples herein were measured by the well-known Gardner method.

.
: -;
. .", . .
. .
18~224B-F -58-:
, ''' ~ ~L ` ' `.~
~, ~

~3~'13 ~X~MPLES
Example 1 - "Solubilization" of DER~-667 by Reacting With 65 Percent or 75 Percent H3P0~ and Neutralizing With Triethylamine. EEW =~2000 3~ _ O _ _ A. The resin i~ dissolved in an equal weight o~
dioxane and the solution mixed at room tempexa-ture with 75 percent H3P04 in an acid/resin weight ratio (13.26/200~) such as to provide 3.0 equivalents of H per e~uivalent of ox irane. A sample of the resulting mixture (number 0) is immediately "quenched" tstored at low temperature) as an analy~içal control sample~ 0ther portions o the mixture are put in each of seven sequentially numbered v~als which are then placed in a 70 oven.
The vials are removed from the oven in number sequence at the elapsed times giuen in the following table and rapidly cooled to "¢uench"
the reaction on-going thereinO
Samæles of the contents are then titrated for oxirane ~EEW3, free H3P04, phosphomono-ester and phosphodiester. The Gardner vis-~osity of each reaction mixture is determined ~ ancl its dispersibility in water~ after neutrali-za~ion with triethylamine, is checked.
Bo Experiment A is repeated, but using an amount (15.3 grams) of the 65 percent acid such as to provide 3 acidic hydroxyls (3 equivalents of H~) per equiualent of the resin, ~" ~
18~224B-F ~59~
.~ .

;'"~
~ ,..'.
~ .

. ~

3~-3~i~

The results of Experiments A and B are summarized in Table 1 :Eollowing.

~'v , ~:
,.

. ~
,' '','' :~ .
.~, .
i: ~

,. , .
;c ~, ,. .
, ~
'" '~;
., .

,:
.,~.
' , .

~ ~ 18, 224B-F -60-,~

, ~-, . .

5, =~

`, ~ i--- . , :

3~i~3 n O ~D ~r N
l u:~ ~ o tu m t~
ul _l Clo ~a~1~n o o I ~ ~ --I tD
a~ d' ~ t~l t~D
a~
~1 a~. Ln ~t~lt~ o t~
r ~1 r~ l t~

t-.¦ ~ tn ~;p ta1`L-~ tn O
l ~
n r ~ t~
t~ ~ otn u~
I ~
~q ~ r o ~ ~r ;~
~n ~ o o r~
~Z; . . .
~1 ~ r t7) p: ~ U~
: r` ~1 o tQOt~l) ~ tS~
~9 tD~ ~ ~
aD ~ Dt'`l 1`
t~
O C~) tr~ ~ ~ O ~ _~
.~ I u~ ~ 1` tD
: ' ~ L~
u~ o t~ tn ~ --I
t5) tD
. ~ Et ~ ~ ~ ?~I` ~ ~ tn . ~ ~ ~ tt~
I tr) ~ tr~ ~D
~C ~D t~ t~l O 1` In ~: a) :: :
C~
t~ ~ qt~
I IJ') tD~
. _l ~`
''` O O ,1 ".;~ ~ 1~ d' O ~ ~ ,,~

.~'' "J ,~, ,~ ~ * ~*
U
u n ta tn : . tn ~D ~ -a h S~ ~U `: td P~ (D
: ~ C~ rl tD Z r~
O ~ 1~ tD ~ U ~ h~ tU t~ O O
tn Q~ D
O ~ ~ 1 tU ~ rl :i Sl U tD C,) X U7 U ~ tD O ~Q X ul O
E~ O C m h Oa1 G ~U O ~
1 o o -1 ~d t~l ~ O ~ O
P V ~ ~ u . .
`~
18, 224B-F' -61-:
.
.,, , ~ , . . .

~3~

Example 2 - Solubilization of DER~-664 by Reacting ~ With 85 Percent or 99 Percent H3PO4, in Dioxane at - Reflux~ and Neutralizing With Triethylamine.
EEW^V1000; H ~Oxirane Ratio - 3:1O
. .. . . .
A. 25 Grams (O.025 equiv.) of DE~-664 was dissolved in 25 grams of dioxane. To the resulting solution w~s added 25 grams (~V0.076 e~liv.) of a 10 percent solution of 100 percent H3PO4 t99 percent allowing ~ lO for some moisture uptake in handling) in ; dioxane. The mixture (solution) was h~ated to reflux (~101), refluxed 3 ho~xs and cooled to room temperature. The acid number ~` of the reaction mixture was found to be 124.05 (versus ]02, thaoretical for adduction of one oxirane group per molecule of H3PO4). No unreacted epoxide could be detected.
~he reaction mixture was extracted with 50 ml of water and the acid content o~ the extract was found (by titration with dilute KOH) o - be 0.013 equivalents. The "rafinate" requir-ed 3 grams (0.03 equivalents) of triethylamine for neutralization. The total acid consumption for the reaction was then 0.076-(0.013~0.030)=
0~033 equivalent, or 0.033/0.025 = 1.32 equi-valent of H~ per oxirane.
:,, ;; B. E~periment A was repeated, except t~at 25 ml o~ a dioxane solution containing 2.94 grams ~ (0.076 eguivalent) of 85~peraant H3PO4 were ,,~i ~,, ~:
''~

, i ",, -- - - . , ~3~ 3 used in place of the acid solution employed ,- in A. The acid number o the reaction mixture was lower ( 108), the acid contents o the ex-. tract and raffinate respectively wexe 0.009 and 0.035 and the ac:id consumed ir. the reaction again~ was 0.033 equivalent.
Both o~ raffinates A and B (after being stripped o~ residual dioxane)~ gave faintly hazy but stable dispersions in water at a solids level ~, 10 of ~1 percent.
Example 3 - Effect of EFW and H /Oxirane Ratio on Solubilization of DGEBA-Type Epoxy Resins by Reaction With 85_Percent ~3 ~ _ _ _ __ _ _ ~: .
Four DGEBA-type resins varying in EEW from 190 to 2000 were separately reacted at 75 in dioxane with , ~ am~unts of 85 percent H3PO4 such as to provide from 0.5 ,~ to 3~0 equivalents of H per oxirane. ~he dispersibility j~ of each re~ction mixture) as such and when neutralized with triethylamine and stripped of solvent~ was checked.
~;~ 20 The results are summarized in Table 2 following. From the data in the table it appears that H to oxirane ratios as low as 0.5 are generally inoperable for the purposes of the present invention.
The data also suggests that ratios above about 1.0 are essential to dispersibility only for resins ha~ing EEW's above about 1000.

, , .
~" . ' . :'~
: ~ -~ 18,224B-F -63- ~

o ~ 3~
~ ~n .~ ~
~D n ( ~g o . . , -~ +
o o ~: ~ o a~
Fi~ . . h a ,, ~ ~
o ~ I
~D ,C
I
. . r~

o ~ .
o ~, u~ I
~D O .
o ,~ ~n O I +
~; o r~
1:1 ~1 ~ h . ~ O ~ +
u~
P

0 ~1 , ~ O
. ~1 U~ U~
.~''` ~ _i ~i D O ~ +
:' ~ U~
O ~
lil . . ~ + +
a ,, . ~. 117 ~ d~ V
:~ ~
,., ~ o,l :o ..
.- ~ U~
tt7 G _I r~
~ ~ ~ +
1~ _I
.` P~ O O ` _ l . ~ t +
a ,~
~, ~ g b~
U~
o . ~ . ~ ~ U ,~
~ h t:~
:, ` , ,g! 0''' ,, v ~ z ~ a p ~ t` ~ 0 ~:
'` q;~~--' X X
~ ~ O O ~ ~ ~
~t:~:l ao ~ + ~ ~:: O
:: ~ m ,a~ O 1~ d X
.:IU ~ I m u) ~ t .- ~¢ ., ~ ~ ~ + ~ + ~ .
~ X ,~
W ~ E`~ ~ U

`
18, 224B-F -64-: `
.

:

3~

Example 4 - Solubiliza-tion of ~E~C~-667 by Reaction . With a Condensed Phosphoric Acid Source Material.
(8 P-O~I Per O.Yirane.) _ _ ~
A solution of 100 grams (0.05 equiv.) of D~R~-667 in 200 grams of dioxane was dripped slowly into a stirring solution of 17.8 grams (0.1 moles) of pyrophosphoric acid (equivalent to 0.2 moles of H3PO4) in an e~ual weight o~
dioxane, the temperature of the reaction mixture being maintained at 80-100C. In about 0.5 hour~ a soft gel had formed. upon addition of another 270 grams of dioxane7 , the gel only partially dissolved, but the resulting mix-~; tura was stirrable. After another 3 hours reaction time, ;, no unreacted epoxide could be detected tin the continuous,liquid phase). Titration of a sample of the gel phase (dissolved in a mixed solvant; 17 percent H2O, 17 percent , ~ methanol and 66 percent methyl ethyl ketone) showed it ,~ to consist largely of DER~-667 in which the oxirane groups had been converted to phosphodiester groups.
~, The reaction mixture was converted to a homo-~` i 20 genous liquid by adding 10 grams (0.56 mole) of water and stirring and heating for 3 hours. Titration of the final solution showed that all diester groups and P-O-P
~;~ links had been hydrolyzed~
Since a good determination of the amount of free phosphoxic acid could not be made by titratio~ an ali~uot of the reaction mixture wa,s repeatedly extracted ~, ~ with water and the combined extracts were titrated. The proportion of the oxirane groups (in the 667) con~erted to phosphomonoester groups was calculated to be 7104 per-~i 30 ce,nt (from the difference between the amount of H3PO4 18J 224B-F ~~5~
~` `

:

; . . ~ , 1~3~

charged (a~ H~P~07) and the final ree acicl content in the aqueous extracts). The proportion of oxirane groups converted to glycol groups was then (by difference) 28~6 percent and the number ratio of glycol to monoest~r groups in the ~inal product was 0.4.
Alt~ough the continuous liquid phase co-formed with the gel was not separately worked up, it was esti-mated from the titration curve ~or this phase that only - about 10 percent or less of the 667-derived product it contained was diester~ the rest being monoestex.
Dispersions were prepared from final reaction mixture samples which had and had not been essentially freed o~ H3P04 (by extraction with water). The samples were neutralized to a pH of 7~5-8.0 with triethylamine, stripped and diluted with water to a non-volatiles level of 16 weight percent~ The unextracted sample gave a viscous, hazy white dispexsion which had good film forming properties. ~he extracted sample gave a water-thin, clear blue dispersion, but the film forming properties of the latter dispersion were poor.
E~ample 5 - Utility of ~eutralized Reaction Products ~; of DER~-667 With H3P04, as Dispersants for a DGEBA
Epoxide Havinq EEW's up to~-13,000.
A. A "high" ester content DER~-667/E3P04 product was prepared by reacting DER3-667 (EEW ~1550), ~: .
~-~ wit:h 1 mole (6 phr) of H3P0~ (as 99 percent ~- a~ueous H3P04) per equivalent of epoxide, in methyl eth~l ketone at 80C for 15 hours. No unconverted epoxide xemained and the glycol 18,224B-F -66-:, to ester ratio was 34/66 - 1/1.94~ This product was ~ixed with successively l~wer amounts of DE~-6~4 solution (40 weight percent solids in ~EK) and each of the resulting mixtures was neutra~ized with two eguivalents of triethylamine~ diluted with 25 phr of methylane chloride and mixed ~ with 100 parts of water per 100 parts of ;~ total resins. The stripped products (emul-sion) contained 50 weight percent total solids and were evaluated as dispersions.
The results are given in Table 3.

~ABLE 3 . ~ DISPERSIBILITY I~ WATER OF
MEUqRALIZED MIXqrURES OF
DER(~-684 AND DER(~-667/6 phr H3PO4 REACTION PRODUCT

DER~-684 phr Quality 2.0 Dispersion grainy, settled on standing.
..
2.6 Rorderline acceptability, slight settling noted.
3.1 Borderline acceptabili~yJ
slight settling noted.
~.1 Good dispersion. No ~ettling~

~; ~O 680 Grams of a 40 weight percent solution of DE~-684 in MæK was heated at 78C for 24 hours with 3.72 grams of pyrophosphoric acid and the amount (O.38 gram) of water requir~d 18,224B-F ~~7~
.: .
.~,: ~ ,.

L3~3 to convert it to 100 percent ~I3P0~ (~ 1.5 phr).
The EEW of the resin never rose above 5~,000 ': (^v74 percent oxiran0 conve:rsion~ and the - neutralized final pr.oduct did not give a .~ 5 dispersion with watexO When the 50,000 EEW
product xesin was sl~stituted for DER~-684 in . the mlxtures of part A aboveJ somewhat poorer ;; dispersibility was observedO
The dispersed mixtures obtained in the experi-ment of part A, at DER~-684 contents of 50 phr and le~s, exemplify a unique and superior embodiment of the present composition invention. Those skilled in the art will appreciate the advantages, in terms o cured coating properties, conferred by the presence of a DGEBA resin lS component having an (average) molecular weight of about 26,000. FurtherJ it is apparent from the ~uite slow oxirane conversion rate obsPrved in the experiment of part B that most or all of the DER~-684 oxirane groups are present as such in the -684 dispersions~ as formed.
,, . 20 The latter groups would not be expected to remain uncon-~:~ ver~ed for an indefinite period of time in the presence -` of both water- and acid-hydrolyzing amine phosphat~e ,:~ groups ~even though the DER~-~84 is dispersedJ rather than dissolved). However, aqueous dispersions of neu-tralized DER~-684 (as such or reacted with H3P04) and DER~-667/H3P04 reaction product mixtures appear to be ~` proparly regardable as highly novel~ oxirane-comprising compositions of matter.
, ~ .
r ~ ~18,224B-F -68-.
.

3~i~3 Ex~mple 6 - neduction of Fre~ Acid Content. In Reaction Product of High EEW DGEB~ Resin With ~6_~r ~3 ~ , to Improve Dispersibili-ty.
~ solution of 9S grams (0.0198 equiv~) o~
DE~-669 (EEW 4800) and 5.88 grams 85 percent H3PO~
~00051 moles H3PO~; 7.73 P-O~ per oxirane) in MEK was refluxed at 80C for 15 hours. The reaction mixture was cooled and sampled for analysis:
Unreacted oxirane content, none;
Oxirane converted to phosphomonoester, 40 percent;
Oxirane con~erted to glycol, 60 percent;
Glycol/ester group ratio, 3/2;
Free H3P04 in product, 4031 grams or 4.27 weight percent of nonvolatiles present.
The reaction mixture was divided into portions.
One portion was neutralized with triethylamine to a pH
o~ 7, dilutad with water and stripped. The stripped material was not a stable dispersion.
A second portion was mixed with enough water (an equal volume of water) to precipitate the polymer.
The liquid phase was decanted and the precipitate tri-~; turated with more water, which was then also decanted.
The polymer was taken up ~n MEK and the solution sampled -~ for analysis. 30 Parcent of the free acid was found to have been removed by washing; the H3P04 present consti-tuted approxi~ately 3 weight percent of the resinous product~ A ~table, opaque, non-grainy dispersion (50 percent solids) was o~tained by neutraliz-ing this product to pH 7 with triethylamine, diluting it with water and stripping of~ the MEK.

18,224B-F -69-'~' ' ' .

.

Example 7 - E~fect on Suhstrate Wettiny of Substituent on ~ nol Used to Cap DGEBA R~sin. _ _ _ DER~-664 was separately reacted wi~h 0.5 molecu-lar propor~ion each of phenol, p-t-butylphenol and p--nonylphenol per equivalent of oxirane. One gram mole c of the phenol reactant, 0.3 gram o~ A-l catalyst ~ethyl triphenyl phosphonium acetatel and 15 milliliters of xylene were added to 250 grams (0.13 g moles) of molten (^V120C) DER~-664 and the mixture heated~ with stirring, to 200C
an~7 refluxed until the EEW was approximately equal to the sum of the molecular weight of the phenol and twice the initial EEW of the resin. The xylene was stripped off, a retain sample taken and an equal weight of MEK
stirred into the residual, capped resin.
~he resulting solution was heated to reflux and 0.5 mole of H3P04 (as the 85 percent aqueous acid) was diluted with an equal weight of MEK and added drop-wise. Refluxing was continued until the E~W was about 60,000 or remained constant. The solution was cooledJ
~ 20 neutralized with 1 mole of triethylamine and diluted i~ with the solids therein. The diluted mixture was stripped with stirring under reduced pressure at 70C until no more MEK came off. The stripped product was a stable ~ aqueous dispersion containing (by analysis) approximately r 25 50 weight percent solids. Portions of the dispersion were diluted ~o 30, 35 and 40 weight percent solids with water.
Brookfield ~VT viscosities were determined for each of ~he four dispersions (12, total) using a !, S~
18,224B-F 70-~ ~ .
'.;
. .. . . .

;43 #4 spindle at 100 rpm. Surface tension~ were measured (average of 5 replicates each) with a Fisher Surface ~ Tensiomat using a 5.990 cm diam. wire circl~.
The wetting abilities of the different disper-sions on three types of substrates were judged by putting a small amount of each of the dispersions to be compared v~ on the same panelg drawiny them simultaneously in parallelwith a #18 wire wound rod and observing the resultant film strips for continuity, "crawling", spreading or shrinking, "beading", "fish eyes" and evenness. Overall ratings of ~: from 1 (best) to 3 (poorest) were assigned~ on the basis of the foregoing visual criteria, within each set.
pH's were checked for all of the dispersions and found to be consistently within the range of 8.45-8.55.
The results of the viscosity, surface tension and wetting evaluations are given in Table 4.

; ~
?

: . .

., , . . , : ' :'' `

18,224B-F -71-.: . . , ., :

~':
,~ tt~ h 3 h 3 al ~a 0 ~
~?: D~ ~ J a) rd ~ td h ~a h~ ~-I ~ ~ O h a) ~ t) q) u 1 J R U~
~ c~ ~ ~
a~ ~ ta ~J
.,1 P~ ~a ~ 3 Sl 3 -~ ~ 3 :~ o al ~rl h ~ 51 ~ ~ h ~rl ~ ~ ~1 U O O ~ O C~
~'~
--I O
aJ~
~-1 ~4 td h ~ ~ ~ 3 ~ ,C 3 1 Zi ~ ~ 3 3 h ~ h U') U

~ P~ U~
o ~P a) ~ ~ ~ ~
.,1 ~-- ~ In u~ In ~ U
0 ~ 0 E~ ~9 ~
~m o o o o o q~ ~ u~ n In In In h ~P,l u~ a7 ao ~i ~Q ~ O O

I -I O O O ~
_ I
.,1_~
~o ~q ~
O Q_ ~1 0 0 0 N
p~ --l ~ ~ ~ ~
.~ m . P _~ . O
~.~ _, ~ o ., ~ _, ~ ~ ~ _l ,..
, ; _ .'~ oq ~ ~ ~ O
o ~n o o o o .: o ~
;
.~ ~ ~ _ ~-,1 ~ ~

..
` 0 ~ ~ .~ O~ E~
o--~ o h ~ ~ h ~ i3 ~Q ~ U r~
V U ~rl ~ O
u~

18, 224B-~ -72 , `
:
... ,~........... ~ .

: .

L3~
.. , ~

It is apparent from Tabl~ 4 that the wet~ing abiiity goes d~n as R20 (in formula (q~) goes ~rom nonyl x to t-butyl to H, the differences being most pronounced (at 35 or 40 percent solids) on a clean aluminum sub-'! 5 strate and least pronounced tat 30 percent solids) on ~ uncleaned cold-rolled steel. These ef~ects roughly corre-:
late with the somewhat higher viscosities and lower sur-face tensions of the nonylphenol-derived dispersion~
Example 8 - Sequential Co-reaction of H3P04 With ,~ 10 DER~-667 and a Phenylglydicyl Ether Substituted With Methylol Groups (Type (b) E2 Epoxide) W - 720; 0~935 P~OH~Oxirane~
70 Pounds (~ 0.02 pound moles) of DER~-667 was dissolved in 100 pounds of methylene chloride and ~ .
20 pounds of IPA, warmed to reflux in 2 hours, and reacted 24 hours at 41 with 5.0 pounds of 85 percent H3PO4. The oxirane content, on a solids basis, was less than 0.1 ,~ percent. 30 Pounds (~J0.1 pound moles) of the ~lycidyl ether of 1,6-bis(methylol)-4-t-butylphenol was then react-; 20 ed in at 41C for 33 hours. The oxirane content again was less than 0.1 percent; acid number 14.5. 175 Pounds of distilled water, and then 80 pounds of triethylamineg were stirred in. After th~ solvents were stripped o~f, the residual dispersion had a p~ of 8.5 and displayed excellent stability and solution characteristics, i.e., no settling, low Opacity and no grain. Coati~gs were applied on aluminum test strips at a non-volatiles level .
of 20 weight percent, in water, using a ~10 wire-wound rod and with no pretreatment of the test strip surfaces.

18,224B-F 73 ~, , :;';
,~,,: , ~3~

,.

Good wetting, excellent ~low and full cure in 8 minutes at 380E (193C) or 5 minutes at 400F ~204C) or 3 minutes at 44GF (227C) were obtained. The chemical resistance of the films was excellent; usually~ 50 acetone double rubs were passed. Excellent wetting was also observed on tin-free steel coupons. No blushing of coatings on either type of surface was observed af~er 30 minutes immer-sion in boiling water. The preceding cure times were cut in half when 1 percent p-toluenesulfonic acid ( solids basis) was included in the water-thinned dispersion~ with no loss of film pxoperties.
Examples 9-12 - Effects on Viscosity, Cure ~ates and Film Properties of Neutralizing Sequential Co-reaction Product With Di~ferent Amines A master batch of acid/El/E2 product was made up in a two-step esterification assentially as i~ Example 2. (EEW of El + E2 = 720; 1.32 P-OH/oxirane.) In the ;~ first step, 700 grams ~0.2 g moles) of DER~-667, in 1000 grams o methylene chloride and 200 grams of IPA, was warmed to reflux in 2-1/2 hours and reacted with 70 grams of 85 percent H3P04 for 41 hours at 41C~ acid number 95;
oxirane content less than 0.2 percent. In the se:cond step~ 300 grams (1.13 g moles) of the glycidyl ether of - 1,6-bis-methylol-4-t-butylphenol was react~d in at 41C
:
- 25 for 16.5 hours. The oxirane content was less than 0.1 weight percent:; acid number 70. 2150 Grams of distilled water was stirred in and the resulting, homogeneous dis-persion was split into ~our equal portions.

.

18,224B-F ~74~

i-.~, Example 9 To 1000 grams of acidic product di~persion was added 27 grams o~ trLmethyl~nine. A~ter stripping, the pH was 7.4~ Coatings prepared and tested as were S the coatings of Example 8 were essentially identical in character thereto.
Example 10 To 1000 grams of dispersion were added 34 grams o a 50:50 blend (by weight) of triethylamine and di-methylaminoethanol; pH = 9, before stripping. The result-ing mixture was a hi~hly viscous gel which, howe~er, could be stripped of solvent easily. The stri~ped dis-persion was not highly viscous and gave coatings, at the same level of non-volatiles, which idff~red from the coatings of Example 9 as follows: Cure at 400F
(204C) required 3 minutes, rather than 5; the coatings ha~ less tendency to dry out before being cured; no aiffer-ence in the effect on cure rate of 1 percent p-toluene sulfonic acid and the viscosity of the water-thinned dispersion was highar.
Example 11 ~o 1000 grams of dispersion, 40 grams of di-methylaminoethanol was added. A highly viscous but readily stripped gel resulted. irhe residual dispersion was diluted with water to a 20 percent content of solids.
Coatings prepared as were the coatings of Example 4 differ-~ ed in the foLIowing respects: Slower cure (5 minutes at ; 400~F (204C), instead of 3 min~tes); acetone resistance ~''' ' ' .

18,224B-F ~75~

somewhat in~erior; almost no tendency to dry out be~ore cur2; much higher viscosity and 1 percent p-toluene-sulfonic acid was less effective in accelerating curing.
Example 12 ; 5 To lO00 grams of dispersion, 35.5 grams of ~ diethylantinoethanol was added. A highly viscous but ; readily stripped gel resulted. After stripping, the residual dispersion was still q~tite viscous and was there-~ fore diluted to 15 percent solids ~rather than 20 perc~nt) y 10 with water. The differences observed hetween coatings ~p prepared from the resultant so]ution and the coatings of Example 9 were as ~ollows: Much higher solution viscO-sity; no tendency to dry out before curing; slower curing ~ (7 minutes at 400F (204C) instead of 5 minutes) and no s 15 improvement in effect of p-toluene sulfonic acid (l per-cent) on cure rate.
t Comparison of Examples 2 and 4 show that tri-methyl and triethyl amines were generally equivalent for neutralization of the co-reaction product. SimilarlyJ
no substantial difference is seen (Examples ll and 12~
between ~ dimethylethanolamine and the N,~-diethyl homo-~ log thereof. Comparison of Example 8 (or 9) and 10 shows r~;' that a 1:1 mixture of triethylamine and ~ dimethylethanol-amine gives a faster uncatalyzed cure rateJ a higher dis-,~ 25 persion viscosity and a reduced tendency for the uncured film to dry out. HoweverJ it is apparent from Examples ll i~ and 12 that t:he use of either of ~ dimethyl- and ~
-diethyl ethclnolantine gives generally poorer results, except for a further decrease in dry-out ~endency.
',' ' ~:
~ 18,224B-F ~76-~ .. ,:, L3~;~13 Example 13 - Inverse Sequential Reaction in Eth~nol of a Nonyl Substituted Monofunctional Type (b) E2 Epoxide and a Bisphenol-F Resin (El) With H3P04.
(EEW - 284); 1.15 P-OH/Oxirane Electro-coatable Product.
.
11~25 Grams (0.096 g mole) of 84 percent aqueous H3PO~ was added to a mixture of 5 grams of ethanol-B
with 38.75 ~rams (0.0965 g mol,e) of the glycidyl ether of 2,6-dimethylol~4-nonylphenol at room temperature. A
slight exotherm resulted. A mixture of 5 grams of ethanol--B and 31.8 grams (0.0965 g moles) of an experimental resin (nominallyJ the diglycidyl ether of bisphenol-F) ~ was then acLded. ~his resulted in an exokherm which rais-3~ ed the temperature of the final mixture to about 100C.The reaction mixture was allowed to cool to and stand at room temperature over a weekend.
67 Grams of the product (89 percent non-volati~es) were stirred with 33 grams of water and the resulting dispersion neutralized (to pH 6.0) with 5.6 grams of di-~` ethylamineO Addition of 10 grams more of ethanol ancL
18~4 grams more of water gave dispersion containing 50 ... .
; weight percent of non-volatiles.
The dispersion was used to deposit a film on tin-free steel by electrocoating. Two steel coupons, each l-lf2" x 4" and spaced 2" apartJ were immersed to a depth of about 3" in the dispersion and 100 volts D.C. ~ !
applied between the coupons (electrodes)O The current drawn-droppecL rapidly (30 seconds3 from an initial value of 150 milliamps to a value of 50 ma. The anode (nega-tive) electrcide was found to ~a covered with a coherent ' .

18,224B-F ~77~
':

:

~ .

;:
coating of the resin. ~ft~r being baked 15 minutes at 175C, the resulting film showed good resistance to boiling water.
A film of the dispexsion was drawn on a tin~
-free steel coupon (not trea~ed to remove oils) and showed excellent wetting. After being baked 10 minu~es at 185C, ! the film was resistant to acetone, showed excellent re-sistance to boiling wa~er and did not crack when the coupon was bent in a 1" radius curve.
When a portion of the dispersion was thinned with water to a non-volatiles content of 5 weight percent, the thinned dispersion approximated a true solution in appearance and action. Films of the thinned dispersion electrodeposited excellently on aluminum and cold rolled steel and,-after being baked 10 minutes at 175C~ showed excellent acetone resistance and withstood 50 inch pounds in the reverse impact testO
Example 14 - Simultaneous Co-reaction o~ DER~-667 (E ) and a Type (m) E2 Epoxide With Phosphoric Acid.
(EEW = 465 0.85 P-OEI/Oxirane.~ _ _ _ _ 420 Grams (0.26 g moles~ of DER~-667 was dissolved in 900 grams of m~thylene chloride and 180 grams of iso-' ~ propanol. 180 Grams (O.286 g moles; 1 equi~.) of heat--fluidized (rv80-l0ooc) DEN~ (D~w Epoxy Novolak) - 438 was stirred in, and then 42 grams of 85 percent H3PO
The mixture was held at room temperature for an hour and t~en heated t.o re~lux (41) and reacted at reflux~for 16 -hours. ~t this point the EEW (~olids basis) was 49000 (percent oxiràne - 43 x 100/4900 = 0.09 ~ percent) and ; ~ ;
:
~ ~ 18J 224B-F -7s3-,~' ~ 3~

the acid number was 53. 800 Grams of distilled water was s~irred in and the resulting dispersion divided into two equal portions. One portion was neutralized with 50 grams of 25 percent aqueous ~aOH and the other portion with 30.5 grams o~ triethylamine. The caustic-neutralized portion was difficult to strip to a solids content higher than 15 wPight percent but both stripped ; products were readily thinnable with water to give stable, homogeneous, grain-free dispersions. DE~ 438 has an EEW of about 180, an epoxide functionality of about 3.5 and is a polyglycidyl ether o~ phenol-formaldehyde novolak.
Product Compositions Versus Water-thinnab lity Gel Permeation Chromatographic analysis has .
~5 shown that only very minor amountsJ if anyJ of oxirane are consumed by reactions other than with water or P-OH
groups and essentially no triester yroups are formed.
Also, only minor amounts, if any, of polyfunctional diesters (esters in which an epoxide molecule is linked through phosphodiest~r groups to more than one other epoxide molecule) are produced in the reaction unless the reaction medium comprises about 75 weight percent or , more of a solvent like dichloromethane.
~; It is evident from the data given in the fore-.
going examples that glycol group formation results not only from oxirane hydrolysis; hydrolysis of ester (phos-. ~ ~
phodiester) groups also proceeds to a limi$ed extent~
although more significantly-at higher~r~action tempera-tures and when more dilute H3~P04 ~is used. Also, direct 18,224B-F -79-.. , ~ ':

f~ L3 esterification of alcoholic hydroxyl groups present as such in El (or formed upon P-OH/oxirane adduction) has a small effect on the total content of phospho-~on~ester~groups in the final pro~uct (after~ say, 3-6 -~ 5 hours reaction time).
It is particularly surprising that solubili-zation (water-thinnability) o resins such as DER~-667 can be achieved by a reaction in which up to about 95 percent of the oxirane groups are converted to glycol 10 groupsJ rather than to acidic, salt forming groups.
DGEBA resins are already polyfunctional in alcoholic hydro~yl groups, but are nevertheless distinctly hydro~
phobic. Conversions of, on an average, one oxirane per molecule to a glycol group would not be expected to 15 noticeably decrease the overall hydrophobicity of the molecule7 Furthermore, conversion of the remaining oxirane groups (somewhat l~ss than one per molecule, on the average) to alpha-hydroxy phosphomonoester groups ~ou d not appear to provide enough salt (neutralized) 20 groups to result in solubilization. Yet, the ~acts are that the oxirane groups in ~he resins are converted al most entirely to glycol and (mono) ester groups and that even at an average content of substantially less than one monoester group per molecule, the neutralized pro-25 ducts derived ~rom El resins having EEW's up ta about 3200 are water-thinnable. It is even more surprising that DGEBA resins having EEW's as high as 5500 can be made water~dispersible by the present process.
., ~' .

18,224~-F -80-.
.;: : , .

~ ~3~

The product will retain its essential chaxac-ter even i~ it additionally contains an amount of phosphodiester groups (each derivable ~rom reaction of a molecule of phosphoric acid with an oxirane group in each of two diffsrent epoxide molecules) in an amount such as to account for up to about 10 percent of the phos-phorous present therein. At some stages of thP process of the present invention, higher proportions of diester groups may be presentJ but such groups tend to hydrol~rze to monoester and glycol groups. Even at room temperature, this hydrolysis reaction will generally continue (so long as any water is present) until little if any di-ester groups remain. Since neutralization is usua~ly carried out in the presence o water, the content of diester groups therea~ter will ordinarily be very low anyway.
; When an acid/epoxide reaction product contain-ing a relatively large amount of free phosphoric acid is neutralized, particularly with an inorganic base, the amount of free acid-derived salt present in the neutral-ized product may be such that the dispersibility o~ the salified resin in what, in effect, is a brine, ra~her than in water, becomes a consideration. However, there are obvious expedients for avoiding this problem and in any case the amount of base in the neutralized pro-duct will be! at least the sum of that consumed by the :':
free acid, and whatever amount is required to salify ~;~` enough ester~P-OHimoieties to-render the resinimolecules ,:
~i dispersible in water.
.,. .~ ' 18,224B-F -81-~, :
'' '`''''' .. , , :

13~a 3 It is apparent, from Exampl~e 5 h~rein, that the utility o~ the present invention may be indirectly extended to DGEBA type epoxides having EEW's a~ high ;: as 13,000' That is, resins of the latter type, such as DER~-684, which do not yie:Ld water-thinnable products when reac~d with phosphoric acid and neutralized, may nevertheless be co-dispersed ~as such or as estexified resins) with (neutralized) reaction products of the present invention~ in water~
On the basis of some experiments not detailed herein, it has been found that the products derived from DGEBA resins having EEW's an order of magnitude lower than DER~-667 are not effective dispersants for DER~-684. However, essentially all of the neutralized ~ 15 . products of the invention are apparently capable of dis-~ persing substantial proportions of unconverted DGEBA
molecules of at least as hi~h an EEW as those the neu-tralized products are derived from. ~eutralized products ;~ of the invention in which up to about 54 percent of the charged oxirane groups remain unconverted can be dispersed ~ in water and give useful coatings~ Assuming a statisti-`~ cal distxibution of the unconverted oxirane groups in the resin molecules~ it is apparent that substantial proportions of molecules having all of their original oxiranes intact are present in such pxoductsO
Thus, composi~ions o~ the present invention as defined earlier herein (see summary of the invention) : additionally may comprise molecules of.ormula (a) in ~`~ which hoth oxiranes are intact or one of them is intact 18,224B-F -82-, '~

.: . . .

`) and the other is replaced by a glycol or betahydro~y phosphomonoester group, the average molecular w~ight of said molecules being not more than about 10 times the averag~ molecular weight of those molecules of .
formula (a~ in which both oxiranes have been replaced by glycol or beta-hydroxyester groupsO ~The ratio of EEW's for DER~-684 and DER~~667 is 13,000/1550 or ~8.4.) `~ ~he proportion of such oxirane-containing molecules present may b~ as much as to provide about one oxirane per glycol or ester group in the composition.
That is, the number of oxirane groups may be as high as ; the total number of glycol and beta-hydroxy phosphomono-ester groups.
The E2-type resins derivable from epoxides of formulas (b) and (p) are highly advantageous for the practice of the present invention. Such epoxides in which R5 is alkyl of from 3 to 10 carbons are particu-larly preferred for the preparation o~ E -derived resins.
Among the latter, those compounds in which p is 1 and R5 is t-butyl or normal nonyl are most preferred as conferring ; superior ability on the mixed E and E -derived resin dispersions to wet hydrophobic substrates, such as aluminum stock which is not oil-free.
~he diglycidyl ether of 2,6,2',6'-tetra(methoxy-methyl)bis-phenol-A is a preferxed alkoxymethyl substituted - epoxide (formula ~1~ for preparation of E2-derived resins (dispersions);).

18~224B-F _83w ' .~
':

' ~ ~

The relative pxoportions of the E - and E --derived resins (salified) ln the composition of the invention can vary widely, depending on the character-istics desired in the end procluct (cured coat~ng, sealerJ
j 5 sllrface active material, primer or whatever). In most applications, an end product whose properties are essen-tially those of the El-derivecl resin will be desired and the mole ratio of El- to E -epoxide-derived species may have a value of up to about 100. However~ in other appli-cations the E epoxide may act more as a modiier than as the main epoxide component and the mole ratio of El--derived to E2-derived species in the end product may have a value down to about 0.1. In those instances where the E2-epoxide (or a l~w molecular weight El-epoxide) under~
goas some oligomerization during reaction with the acid, each monomer unit in the oligomer is counted as an indivi-: : dual molecule in assessing the El/k2 ratio.
.~: The content of free (unesterified) phosphoric acid in the mixed products can vary from none up to about 85 parts by weight per hundred parts of epoxide-derivable : molecules. However, unless the contemplated end use of .~ the salified~ mixed product requires enhanced fire retard-~.~ ancy or the ability to release a substantial amount of :. a dissociable base (to a strongly acid environment or u~on heating) J "free" acid contents of more than about 5 weight percent will generally be undesirable and contents ~: of about 1 part by~weight or less of H3PQ4 per hundred parts of epo.xide-~erivable (or -de~ived) molec:u~-es~will be preferable.
', : . 18, 224B-F --84-.-,

Claims (10)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for making water-thinnable, base-neutralized acidic resins which are convertible to hydro-phobic, high performance, thermoset resins, said process comprising:
(I) reacting orthophosphoric acid with (1) a polyether epoxide resin E1 consisting essentially of molecules of the formula:

or wherein Q, independently, in each occurrence, is:

or , n is an integer of from 0 to 40, r is zero, 1 or 2 and independently in each occurrence, R1 is H, methyl or ethyl, R2 is -Br, -C1 or a C1 to C4 alkyl or alkenyl group, R3 is a C1-C4 alkylene or alkenylene group, ?C(CF3)2, , -SO2-, -S-, -O- or a valence bond, R4 is -Br, -C1 or a C1 to C4 alkyl or alkenyl group, and R20 is H or alkyl of 1 to 12 carbons, said reaction being carried out by contacting E1 with an orthophosphoric acid source material and from 0 to about 25 molecular proportions of water per molecular proportion of H3PO4 provided by said source material, until the fraction of the oxirane groups in E1 converted is at least sufficient to render the resulting product water-thinnable when contacted with a base, the amount of orthophosphoric acid included as such in said source material, or obtainable therefrom by hydrolysis, being such as to provide at least 0.3 P-OH groups per oxirane group, and (II) contacting the resultant reaction product with at least sufficient of a base to render it water-thinnable.

2. The process of claim 1 wherein additionally E2, a vicinal epoxide other than one of formula (a) or (q), which has an epoxide equivalent weight (EEW) of from 90 to 2,000, is reacted with an orthophosphoric acid source material and contacted with a base in the same manner as the polyether epoxide resin E1, and the mole ratio of E1 to E2 epoxides is from 0.1 to 100.

3. The process of Claim 1 or 2 wherein dioxane, methyl ethyl ketone, acetone or a mixture of dichloro-methane and acetone containing 25 weight percent or less of dichloromethane is employed as a medium for the phos-phoric acid/epoxide reaction.

4. The process of Claim 1 or 2 wherein the base is an amine of the formula NR3, each R is indepen-dently H, methyl or ethyl.

5. The process of Claim 2 wherein E2 is one or more of formulas (b) through (p):
(b) a methylol-or alkoxymethyl-substituted phenylglycidyl ether of the following formula:

wherein Y is H or a C1 to C4 alkyl or alkenyl group, each YO-CH2- group is either ortho or para to a glycidyloxy group, X is 1, 2 or 3, p is 0 or 1 and a is 1 or 2, R1, independently in each occurrence, is H, methyl or ethyl, R5 is a C1-C12 alkyl, alkenyl, cycloalkyl, phenyl, alkylphenyl, phenalkyl, phenoxy, -Br, -C1 group or a group, wherein y is 0, 1 or 2 Y and R1 are as above defined, T is a C1-C4 alkylene or alkenylene group, ?C(CF3)2, -SO2-, -S-, -O- or a valence bond, R6 is -Br, -C1 or a C1-C12 alkyl, alkenyl, cycloalkyl, phenyl, alkyl-phenyl, phenalkyl or phenoxy group, and t is 0 or 1;
with the proviso that (x + a) cannot exceed 4 and (x + y) is from 2 to 4;
(c) a methylol- or alkoxymethyl-substituted, (2,3-epoxy)propylbenzene of the formula:

wherein:

b is 1 to 3, d is 0 or 1, R7 is C1-C12 alkyl or , Y' is H or a C1 to C4 alkyl or alkenyl group, R1 is H, methyl or ethyl, with the proviso that (b + d) cannot exceed 3;
(d) di- and trioxides of acyclic or cyclic, C4 to C28 hydrocarbons or esters containing two or three nonaromatic, carbon-to-carbon double bonds and, optionally, a -Br, -C1 or -F or hydroxy substituent;
(e) epoxy ethers of the formula R8-O-R9, wherein each of R8 and R9 is the same or a different monovalent radical derivable by abstraction of hydrogen from a C3-C12 aliphatic-, alicyclic-or phenalkylene-oxide;
(f) 2,3-epoxypropyl halides, alcohols or esters of the formula:

wherein A is -C1, -Br, -OH or , R1 is -H, -CH3, or -C2H5 and R21 is a C1-C15 hydrocarbyl group;
(g) glycol monoethers of the formula:
and glycol diethers of the formula:

wherein, R1 is -H, -CH3 or -C2H5, R10 is -H or -CH3, X is -H, -CH3 or -C2H5, g is 1, 2 or 3 and h is an integer of from 2 to 10;
(h) diglycidyl ether or esters of the formula:

wherein R11 is a divalent hydrocarbon radical of from 2 to 20 carbons, R1 is -H, -CH3 or -C2H5 and i and j independently are 0 or 1;
(i) mono or diglydicyl ethers of and (j) mono-, di- or triglycidyl ethers of glycerine;
(k) trifunctional aromatic epoxides and ; wherein Z is , R12 is C1-C2 alkoxy, C1-C6 alkyl or C2-C6 alkenyl, R13 is H, C1-C12 alkyl or C2-C12 alkenyl, R14 is a C1-C8 alkyl, alkenyl, cycloalkyl, cycloalkenyl or aralkyl group, ortho or para to those Z-CH2- moieties on the benzene ring to which said group is attached, R1 is as previously defined and R15 is a C1-C4 alkylene or alkenylene group or -SO2-;
(1) tetraglycidyl ethers of the formula:

wherein R16 is a C1 to C6, divalent aliphatic hydrocarbon radical, , ?C(CF3)2, -SO2-, -S-, -O- or a valence bond and Z

is ;

(m) tri- to pentafunctional epoxy novolaks of the formula , wherein p is 1 to 3, R17 is H or -CH3, independently in each occurrence, R18 is an alkylene group of 1 to 4 carbons and Z is ;

(n) methylol substituted, oligomeric monoepoxides of the formula:

wherein u is 0, 1, 2 or 3, R1, independently in each occurrence, is H, methyl or ethyl and R19, independently in each occurrence, is a C1-C12 alkyl, alkenyl, cycloalkyl, phenyl, phenalkyl or alkylphenyl group;

(o) epoxidized triglycerides of unsaturated fatty acids of up to 18 carbons each; and (p) one to one adducts of substituted phenols with diglydicyl ethers of substituted bis--phenols, of the formula:

wherein R1, R2, R3 and r are as defined in preceding formula (a), Y, R5 and p are as above defined in formula (b), v is 1, 2 or 3 and w, independently in each occurrence is 0, 1 or 2.

6. A water-thinnable, resinous phosphate compo-sition comprising:
(A) resin molecules, each of which is deriv-able by conversion to 1,2-glycol- or beta-hydroxy phosphomonoester groups of the oxirane groups in an E1 epoxide rep-resented by one of formulas (a) and (q) in Claim 1, the average EEW of the epoxide molecules from which the resin molecules are derivable being from 172 to 5,500, (B) from 0 to 85 parts by weight of ortho phosphoric acid (H3PO4) per 100 parts by weight of the resin molecules, (C) a base, in such amount that at least enough of the P-OH moieties in the resin molecules are salified thereby to render the molecules dispersible in water.

7. The composition of Claim 6 additionally comprising other molecules, each of which is derivable by conversion to 1.2-g1ycol- or beta-hydroxy phospho-monoester groups of the oxirane groups in E2, a vicinal epoxide other than those of formulas (a) and (q), having an EEW of from 90 to 2,000, and the mole ratio of the E1-derivable molecules to E2-derivable molecules being from 0.1 to 100.

8. The composition of Claims 6 or 7 wherein the number ratio of glycol to monoester groups in each of the types of molecules is from 0 to 18.

9. The composition of Claim 7 when applied as a film or coating on a substrate.

10. The coating of Claim 9 wherein the compo-sition is dehydrated, desalified and cured in place on the substrate by heating.