CA1122607A - Derivatives of ester diol alkoxylates and compositions thereof - Google Patents

Abstract

ABSTRACT OF INVENTION

Derivative of esterdiol alkoxylates obtained by reaction thereof with an isocyanate, as well as the anhydride capped products thereof. Formulations containing the above are also claimed.

Description

i07 11855-C-1 BACICGRO~'ND OF THE IN\'E~TIOI~

Governmental reg~lations have plaeed ever increasing restrictions on the amounts and eypes of os~,anic volatiles permitted to escape into the st s-phere from coating compositions. Considerable efforts have been expended to develop coatings compositions having a mi nimal ~mount of volatile organic components and this hss led to the development of powder coatings, radiation-curable coatings, and water-borne coatings.
Yigh solids coatings represent another ~ttractive technology to reduce solvent emissions. In ~hese re-cen~ developments, the amounts of organic solvents present are minimal ~nd consquently there is little or no atmospheric pollution.
A compound often used in the production of coating and ink formulations is 2,2-dimethyl-3-hydroxypropyl 2,2-dimethyi-3-hydroxypropionate (also known as ED-204). ~owever, the ~ormally solid ~ature of ED-204 and other ester ~iol5 has on occasion ~0 presented some problem~ in use. It has been recently discovered that ester diols can be reacted with al~ylene o~ides to form liquit vehicles which, depending upon the particular alkylene oxide selected~ can be either water soluble or w~ter insoluble; these have been called ester di~l alkoxylates. ~ny further discoveries that would al90 serve to lower atmospheric pollution would be of interest for use in industry.

)7 11855-C-l S~S~RY OF THE Il~.~ION

It has now been found that certain deriva-tives of the ester diol elkoxylates can be produced - thst are useful in the production of coating and ink formulations. Ihese derivatives are obtained by re-acting an ester diol alkoxyla~e with an intramolecular polycarboxylic acid anhydride, or an organic poly-isocyanate, or a polyepo~ide, or combinations thereof.
The resulting products have been found useful in the production of high solids compositions. These high solids compositions additionally contain cross-linkers and can contain pigment, solvents, flow control agent, plus any of the other additives conventionally present in a coating or ink. They can ~lso be blended with other polymers and latexes to yield compssitions that pro~
duce dry films having accepta~le proper~ies.
D ~ ~]~
The ester diol alk~xylate derivatives, as well as the ester diol alko~ylates themselves, and the methods for their production ~re discussed in de-tail below.
The Ester Diol Alko~Ylates II
~ he ester dioL alko~ylates belong ~o a new class of ~terials ~ust recently discovered and the subject matter of a different application. These ester diol alkoxylates are psoduced by the reaction of an es~er diol of the structural formula:

11855-C-l R R
1. HOCnH2nCcn~2nOocccnH2noH
R R

with an oxirane co~pound, preferably an alkylene oxide, to produce the ester diol alkoxvlate of the structural formula:
R R
II. H(OCmH2m)xOCnH2nCCnH2nOOCCCnH2nO(C2H2~0)yH
R R

wherein m is an integer having a value of from 2 to 4, preferably 2 or 3; n is an integer having a value of from 1 to 5, preferably 1 to 3 and nost preferably 1; x and y are integers each having a value of from 1 to 20, preferably 1 to 10; R is an unsubstituted or substituted, linear or branrhed alkyl group having from 1 to 8 carbon ato~s, preferably 1 to 3 carbon atons. The subseituents on the R group can be any inert group that will not interfere with the reaceions involved and can be, for example, cyano, halogen, alkoxyl, nitro~ tertiary amine, sulfo, etc. In the formulas, the variables R, m, n, x and y ca~ be the same or different at the various locations.
The novel est~r diol alkoxylates (II) are pre-ferably produced by the catalytic reaction of an ester diol ~I) with an alkylene oxide or mixtures of alkylene o~ites at an elevated te~perature as more fully discus-sed below. One can ~anufaceure the mono, mixed, bloc~ed or capped adducts.

~ 7 11~55-C 1 The alkylene oxides suitable for use in the produotion of the ester diol alkoxylates sre the oxirane com~ounds such ~s styrene oxide, ethylene oxide, 1,2-pro-pylene oxide, 1,3-propylene oxide, 1,2-butylene oxide, ~
1,3-butylene oxide and 1,4-butylene oxide as well as similar higher aliphatic noepoxides.
The ester diols of ~orm~la I include 2,2-di-methyl-3-hydroxypropyl 2,2-dimethyl-3-hydroxypropionate;

2,2-dimethyl-4-hydroxybutyl 2,2-dimethyl-3-hydroxypro-pionate; 2,2-dimethyl-4-hydroxybutyl 2,2-dimethyl-4-hy-droxyb~tyrate; 2,2-dipropyl-3-hydroxypropyl 2,2-dipropyl-

3-hydroxypropionate; 2-ethyl-2 butyl-3-hydroxypropyl 2-ethyl-2-butyl-3-hydroxypropionate; 2-ethyl-2-~ethvl-3_ hydroxyprowL 2-ethyl-2-methyl-3-hydroxypropionat~;
and the like.
Dur~ng the reaction of the ester diol I with the alkylene oxide a catalyst is preferably used in a catalytically effective amount. Ihe amount of catalyst is fr~m 0.01 to 5 weight percent, prefera~ly from O.OS
tQ 0.5 we~ght percent, based on the combined weights of ester diol I and alkylene G~ide. The cstalysts useful are known to those skilled in the art of alkylene oxide addition chemistry and require little further discussion here. Illustrative thereof one c~n mention boron tri-fluoride etherate, potassium~ potassium hydroxide, sodi sodium hydroxide, Lewis ~cids, sodi~m ethoxide, mineral acids, and the like.

il;~'~ti()7 11855-C-l The re~ction of the ester tiol with the slkylene oxide is carried out at a temperature of from 20 to 150C, preferably from 50 to 120~C. for a period of time sufficient to complete the reaction between the - reactants char~ed. The temperature is often dependent upon the particular catalyst selected and the alkylene oxide em~loyed. ~he time will vary depending upon ehe size of the batch and the particular reactants ~nd cat-alyst~ and the rea~tion conditions employed.
The reaction can be conducted at subatmospheric, ~tmospheric or superat spheric pressure. The pressure is not critical and sufficient pressure is generally used to retain the reactants in the reactor in liquid form.
The a unt of alky~ene oxide charged to the re-action i9 from about 2 les to about 40 les, or re, per mole of ester diol charged; preferably from 2 to 20 ~oles.
To minimize oxidative side reactions the re-action ~s preferably carried out under an inert ~s at-~DspherP using nitrogen, argon or other inert gas.

If desired an inert solvent such as toluene, ben-ze~e or l,l,l-trichloroethane can be employed. However, ~he reaction proceeds well in the absence of any such sol-vent. In most ~nstances a solvent is not required as the ester diol is itself a liquid at the elevated temperatures employed and serYes ~o maintain a liquid reaction system.
At the conclusion of the reaction the product, consisting of a mixture ~f the novel ester diol ll'h'~C~7 ll8 j5-C -alkoxylates, is recovered as ~ residue pr~duct and can be used 85 such; distillation pr~cedures ca~ ~lso be used to recover more refined products.
The ester diol alkoxyl~tes can be used as _ ~olvents, vehicles in paint or ink formulations, water-bosne coatings, as an intermediate in the production of other valuable c~mpounds and as a ~urfactant as well as i~ producing the derivatives of this invention.
In a typical ~mbod;~nt, the ester diol and catalyst are charged to the reactor and the alkylene oxite is then ~dded over a period of time while main-taining the desired temperature and pressure. At the com~letion of the addîtion the c~ntents of the reactor are maintained at the selected eonditions until substan-tially all of the alkylene o~ide has reacted. The produc~
can then be purified, if desired, ~nd recovered by con-venti~nal proceduresO In SQme instances one m~y obtain a product containing other glycols as by-products. This can be ~ nimized by proper selection of reaction conditions and catalyst.
The Anhydride Modified Ester Diol Alkoxvlates III
~ he catalytic reaction of the ester diol alkoxy-lates of formula II with an intramoleculas polycar~oxylic acid anhydride produces ~ derivative that contains ~ree carboxyl groups. This oan be illustrated by ~he following formula, in which phthalic anhydride is ~mrloyed for il-lustrative purposes, that shows the resultant product i07 11855-C-l ~OOH F~
~ COO~ 03C ~

obtained by the re~ction of two mDles of phthalic ~ snhydride per le of ester diol ~lkoxylate II.
Illustrative ~f suitable polycarbo~ylic acid anhydrides that can be used one can mention trimellitic ~nhydride, tetrahydrophthalic anhydride, ~hthalic anhydri~e, benzophenone dicarbo~ylic ~cid anhydride, succinic anhydride, maleic aDhydride, lD ~aphthoic anhydrite, ~lutaric ~nhydride, or any other intramolecular anhydride, including those having sub-stituents thereon such as halogen atoms, alkyl or alkoxy groups, ~itro? carbo~yl,aryl, or any other - group which will not unduly interfere with ~he reaction.
The ~m~un~ of polycarboxylic acid anhydride re cted with ~he ~6ter diol alkoxylate II ca~ be an Emount sufficient to permit reaction with all of the hydroxy groups; however, it ~s preferred to use ~n a~ntwhich ~s insufficient to re~ct with all of the hydroxy roups present in the ester diol alkoxylate II

or derivative there3f. This ~mount will vary and can be from 0.1 to 1 anhydride equivalent for cach hydroxyl equivalen~ or group present in the ester diol Alko~y-late II initially charged to the reaction mixture ~nd is preferably from 0.1 to 0.6. In a m~st preferred in-sta~ce, ~ne anhydride equival~nt ar anhydride moiety ~ 7 118~5~

is charged for each hydroxyl equivalent or group ln-itially present in the reaction mixture. I~ ~he react~on a conventional esterification catalvst can be used. Ihese are well known to ~hose skilled in the art.

The ester diol ~lkoxylate II is reacted with the polycarboxylic acid slihydride at a temperature of from about 75 to 200C, preferably from about 100C to 150C. The time required for reaction will vary depend-ing upon the particular reactants charged, the temperature,and the batch size of the reaction mixture, facts which are ~ell known to those skilled ~n the art. Generally9 it has been found th~t a reaction period in the Labora-tory of from 15 to 6Q minutes at from 125 to 150C is adequate to produce the initial carboY,yl-modified ad-dition reaction pr~duct obtained by the reaction Or these two intermediates.
The anhydride modified ester diol alkoxylate III of this reaction is a viscous liquid, in st in-stances. However, in some instances it has been observedthat the product will solidify upon standing at room tem-perature for gn extended period of time. miS, however, does ~ot detract from its ~ur~her utility. Generally, these modified adducts are soluble in both wster and solvents.
e Isocyanate Modified Ester Diol Alkoxylates IV
The c~talytic reaction of the ester diol alkoxyl&tes II with a polyisocyanate produces a hydroxyl Z~ 7 11855-c-ter~inated de~ivative that contains urethane gr~ups IV.
This can be illustraeed by the following equation, in which OC~ CO represents 8 diisocyanate, and shows the reaction of 2 moles of II with one mole of a diisocya-nate: O

2 II ~ OCNXNCO ?II-OCNHXHNCO-II
(IV) The polyisocyanates that C&n be used in this invention ~re well known to those skilled in the art and ~hould not require detailed description herein. Any of the polyisocyan tes c~n be used alone or in admixture with other isocyanates including the noisocyanates.
Illustrative thereof one can mention methyl isocyanate, ethyl isocyanate, chloroèthyl isocyanate, chloropropyl i~ocyanate, chlorohexyl isocyanate, chlorobutoxypropyl isocyanate, hexylisocyanate, phenyl isocyanate, the o-, m-, and p-chlorophenyl isocyanates, benzyl isocyana~e, ~aphthyl i~ocyan~te, o-ethylphenyl isocyanzte, the di-chlorophenyl isocyanates, butyl isocyanate, n-propyl isocyanate, octadecyl isocyanate, 3,5,5,-trimethyl-l-isocyanato-3-isocyanatomethylcyclohexane, di(2-isocya-natoethyl)-bicyclo-(2-2-1)-hePt-5-ene~3-dicarboxylate~
2,4-tolylene diisocyanate, 2,6-to~ylene diisocyanate,

4,4'-diphenylmethane diisocyanate, dianisidine diiso-cya~ate, tolidine diisocyanate, hexamethylene diisocya-~ate, dicy~lohexyl-4,4'-methane dii~ocyanate, cyclohex2ne-1,4-diisocyanat~, 1,5-naphthylene diisocyanate, 434~-diiso-cy~nato diphenyl ether, 2,4,6-triisocyanatotoluene, 4,4', 10 .

1185~ -C-l 4"-triisocyanato ~riphenyl ~e.hane, di?henylene-4,4-diiso-cyanate, the polymethylene pol~?henylisocya~ates as well as sny of the other organic isocyar.ates known t~ the average skilled chemist.
The ~mount of ester diol alkoxylate II used can - be an a~ount sufficient to permit reaction of the isocvanato ~roup with up to about 0.9 equivalent to the total number of hydroxyl groups present. Thus, fro~ 0.025 to 0.9 isocyanato equivalent is reacted pe~ hydroxyl 10 equivalent, preferably from 0.04 to 0.5 isocyanato equi~alent per hydroxyl equivalent, and most preferably from 0.04 to 0.25 isocyanato equivalent per hydroxyl equi~alent initially charged. The conventional urethanP reaction catalvsts are used.
The reaction of ester diol alkoxylate II with isocyanate is conducted at a temperature of fro~ about 25C
to 100C preferably from about 40C to 60C. The time required will vary depending upon the particular reactants char~ed, catalyst, te~perature, and the batch size of the 2~ reaction mixture, facts ~hich are well known to those ~killed in the art. Generallv, it has been found that a reaction period of from 1 to 5 hours at from about 40 to 60C, is adequate to produce the urethane-mGdified product.
This product IY can be used per se or it can be capped or modified with a carboxylic acid anhydride by the reaction o~ this hydroxyl terminated isocyanate modified ester diol alkoxylate IV with an intramolecular carboxylic acid anhydride by the same procedure~ here-inbefore described for producing the anhydride modified ~ Z~07 11855 ~-1 ester diol alkoxylates III. In this instance the com-pounds produced can be represented by the general schematic formula:

IV A
COOH O COOH
- b--COO~ OCNHX`lHCO-II-OOC ~

which shows the product obtained by the reaction of IV with phthalic ~nhydride when fully capped.
The EPoxide Modified Ester Diol Alkoxylate~ V
The catalytic reaction of the ester diol alko~ylate II with a diepoxide Plso produces a hy-droxyl terminated derivative. This can be illustra-ted by the following equation in which two moles of II react with one mDle of a diepoxide ~o prod~ce V:

2 TI + ~ ~ V ~

~1 ~
II ~ O . ~ O - II (V) OH OH

in which,~
~~ ~V
2~ represents a diepoxide.

12 .

The diepoxides that can be used in this invention are well Icnown to those skilled in the art and are fully described in U.S. Patents 3,027, 357; 3,890,194; and 2,890,197. Of particular in-terest is that portion of U.S. 3,027,357 begin-ning at column 4, line 11 to column 7, line 3B.
Among some of the specific illustrative diepoxides disclosed herein one can mention 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate, bis(3,4-epoxy-6-methylcy~lohexylmethyl) adipate, bis(2,3-epoxycyclo-pentyl? ether, vinyl cyclohexene dioxide, 2-(3,4-epoxy-cyclohexyl~-5,5-spiro-(2,3-epoxycyclohexane)-m-dioxaneJ
bis~3,4-epoxycyclohexylme~hyl)adipate, and the like.
The cycloalipatic diepoxides are preferred.
The amount of diepoxide charged to the re-action can vary from about 0.2 mole per mole of ester diol alkoxylate II initially charged to the reaction to as high as one mole of diepoxide per mole of ester diol alkoxylate II. Preferably i~ is from about 0.3 to 0.6 mole of diepoxide per mole of ester diol alk-oxylate II initially charge Conventional epoxide reaction catalysts are used.
Reaction of the ester diol alkoxylate II
with an epoxide is conducted at a temperature of from about 100CC to 250C, preferably from about 140C to 160C

~,.' 1, ~ 7 11855-C-l in the presence of the known c~nventi~nal cat~lysts.
m e tLme requ$red will vary depend~r.g upon the par-eicular reactants charged, catalyst, temperature, and batch size of the reaction mLxture, facts which are well known to those skilled in the art. Generally, lt has been f~und that a re~ction period of from 2 to lQ hours from ~bout 140 to 200C, is adequate to pro-duce the epoxide-modified product. This product can be used per se or ie can be capped or modified with a carboxylic ~cid anhydride by the reaction of this hy-droxyl terminatet epoxide modified ester diol alkoxy-late V with an intramolecular carboxylic acid anhydride by the same procedures hereinbefore described for pro-ducing the 2nhydride modified ester diol alkoxylates III.
In th~s i~stance the compounds produced can be repre-~ented by the general ~chematic formula:
V A

COOH COOH

~COO~ O /~ OOC ~J
OH OH

which shows the product obtained by reaction of V with phthalic anhytride when fully capped.
Fcrmulated ComPositions Usin~ PolYols The dified ester diol alkoxylate derviatives of the types represented by formulas III, IV, IV A, V
and V A can be formulated to produce coating and ink 14.

~ 7 11855-C-l compositions by the addition thereto of crosslinkers, polyols, pigments, fillers, ~nd other additives con-ventionally used in the production of cDatings and ~nks.
In producing ehe formulated compositions a crosslinker such as a ~ethylolated mel~ine can be used in an amount from 25 to 200 weight percent, pre-ferably from 25 to 100 weight percent, of the modified ester diol alko~ylate charged. These compounts are well known and m~ny are commercially available. Those suitable for use can be represented by the general formula:

J~ J~
v~rJ N ~"2 wherein X is hydrogen or -CH20CH3 and wherein ~t least two of the X substituents ar,e -CH20CH3 groups. The preferred melæmine derivaeives are the highly methyl-2Q ola~ed melamines) with hex~methoxymethylmelamine mostpreferred. Other amino resins that can be used include the urea znd benzoguanamine resins.
In addition one can have present a non-volatile low lecular ~eight polyol containing from 2 to 6, preferably 2 to 4 hydroxyl groups. m ese ncn-volatile low lecular weight polyols can have a molecular ~eight of from 62 to about 1000. They can be aliphati~ cyclo-~liphatic or ~rom2tic in nature. Illustrative thereof one ~an mention ethylene glycol, diethylene glycol, tri-ethylene glycol, propylene gylcol, dipropylene glycol, 11855-C-l neopentyl ~lycol, butyle~e glyc~l, 2,2-d'meehyl-3-hydroxypropyl 2r2-d~mPthyl-3-hydroxypropiondte, 2, 3-dibromo-1,4-but-2-ene diol, bisphenol- A and the ethylene o~ide ~nd/or propylene oxite adducts there-of, 2,2-dihydroxy~ethylpropionic ac~d, trimethylol ethane, trimethylol propane, pentaerythr$tol, di-pentaerythritol, glycerine, sorbitol, hydrogena~ed bisphenol-A; l,l-dihydroxy methane cyclohexane, 2,2'-dihydroxymethylbicyclo [2.2.1~heptane, 1,5-pentane diol, decane diol, and the like. Many other non-volatile low molecular weight diols having a molecular weight of fr~m 62 to about 1000 are known and can be used; the above enumerati~n is illustrative ~nly.
Further, one can have present any of the known polycaprolactone polyols that are co 2 ercially a~ailable and ~hat are fully described, ~or eYample ln U.S. 3,169,94~. As described in this patent the polycaprolaceone polyols sre produced by the catalytic polymerization of sn exces of a caprolactone and an organic polyfunctional ~nitiatDr having at least two reactive hydrogen atoms. The method for producing the polyc~prolactone polyols i~ of no consequence and the organic functional ini~iator~ can by any polyhydroxyl - compound aR is ~hown in U.S. 3~169J94~. Illustr~tive thereof ~re the diol~ Cuch as ethylene glycol, diethyiene glycol, ~riethylene ~lycol, 1,2-propylene glycol,`dipro-pylene glycol, 1,3-propylene glycol; polyethylene ~lycol, polypropylene glycol, poly ~oxyethylene-oxypropylene) glycols, and sim~lar polyalkylene glycols, either block-ed;
capped or heteric, containing up to about 40 or more 16.

~ 7 118jS-C-l alkyleneoxy units in the molecule~ 3 methyl-1-5-pentane-diol, cyrlohexanediol, 4,4'methylene-bis-cvclohexanol, 4,4'-isopropylidene bis-cyclohexa~ol, xylenediol, 2-(4-hydroxymethylphenyl) ethanol, 1,4 butanediol, and the like;
triols such as glycerol, t~imethylolpropane, 1,2,6-hexane-~ triol, triethanolamine, triisopropanola~'ne, dr.d the like;
tetrols such as erythritol, pentaerythritol, ~,N,N',N'-tetrakis (2-hydroxyethyl)ethylene diamine, and the like.
lQ When the organic functional initiator is re-acted with the caprolactone a reaction occurs that can be represented in its s~mplest form by the equation:
O
R '(OH)X + 0~1 ~CHR' ~ R"( [OC(CR 2)4CHR ]mOH)X
O
In this equation the organic functional initiator is the R"-(OH~ compound and the caprolactoné is the O~C(CR'2)4CHR
~

compound; this c~n be caprol2ctone itself or a substituted csprolactone wherein R' is an alkyl, alkoxy, aryl, cyclo-alkyl, alkaryl or aralkyl group having up to twelve car-bon atoms and wherein at least sLX of the R' groups are hydrogen atoms, as shown in U.S. 3,169,945. The poly-caproLactone polyols that are used are shown by the formu-la on the right hand side of ~he equation; they can h ve an svera~e molecular weight of from 290 to about 6~000.

11~55 ~-1 ~he preferred p~lycapr~lsctone polyol compounds are those having an avera~e molecular weight of from about 290 to about 3,000, preferably fr3m sbout 300 to 1,000. The m~st pref~rred ~re the polycaprolactDne diol compounds having an sverage lecular weight of from 290 to about 500 and the polycaprolactone triol com~ounds having an average molecular weight of from about 300 to about 1,000;
these are st preferred because of their low viscosity properties. In the formula m is an integer representing lD the average number of repeating units needed to produce the compound havin~ said molecular weights. The hydroxyl number of the polycaprolactone polyol can be from about 15 to 600, preferably from 200 to 500; and the polycapro-lactone can have an average of from 2 to 6, preferably 2 to 4, hydroxyl groups.
Illustrative of useful polycaprolac~nes that can be used in the formulated com~ositions oRe can men-tion the reaction products of a polyhydro~yl compound having an average from 2 to 6 hydro~yl groups with capro-lactone. The manner in which these type polycaprolactonepolyols is produced is shown in U.S. 3,169,945 and many ~uch com~ositions ~re commercially available. In the following table there are listed illu~trative polycapro-lactone polyols. The first column lis~ ~he Gr~anic funct~onal initiator that is reacted with the caprolac-tone ~nd the average molecular weight of the polycapro-lactone polyol is shown in the second column. Knowing the molecular wei~hts of the initia~or and of-the poly-~ 7 11~55 C-l c~prolactone polyol one can readily determine the average number of mDlecules of caprolactone (CPL Units) that reacted to prDduce the polycaprolactone polyol;
this figure is shown in the third column.
IYPE A POLYCAPROLACTONE POLYOLS

Average Average No. -.
M~ ofof CPL units Initiator ~olyolin m~lecules 1 Ethylene glycol 290 2 2 Ethylene glycol 803 6.5 3 Ethylene glycol 2,114 18 4 Propylene glycol 874 7

5 Octylene glycol 602 4 Decalene glycol 801 5.5 7 Diethylene glycol 527 3. 7 8 Diethylene glycol 847 6.5 9 Diethylene glycol 1,246 10 Diethylene glycol 1,998 16.6 11 Diethylene glycol 3, 526 -30 12 Triethylene glycol 754 5. 3 13 Polyethylene glycol (MW 200~* 713 4.5 14 Polyethylene glycol (M~ 600)* 1,398 7 Polyethylene glycol (MW 1~00)* 2,868 12 16 1,2-Propylene glycol 646 5 17 1,3^Propylene glycol 988 8 18 Dipropylene glycol 476 3 19 Polypropylene glycol (MW 425~* 835 3.6 Polypropyle~e glycol (~W 1000)*1,684 6 21 Polypropylene glycol (~ 2000)* 2,456 4 22 Hexylene glycol 916 7 23 2-Ethyl-1,3-hexanediol 602 4 24 1,5-Pentanediol 446 3 1,4-Cyclohexanediol 629 4.5 26 1,3-Bis(hydroxyethyl)-benzene736 5 27 Glycerol 548 4.
2~ 1,2 ,6-Hexanetriol 476 3 29 Trimethylolpr~pane 590 4 30 Trimethylolpropane 750 5.4 31 Trimethylolpropane 1,L03 8.5 32 Triethanolami~e 890 6.5 33 Erythritol 920 7 34 Pentaery~hritol 1,219 9.5 * - Average lecular weight of glycol.
The stru~tures of the compounds in ~he above tabu-lation are obvious to one skilled in the art b~sed on lg.

the information given. The structure of compound No.

7 is:

O
~ 10[(C~12)5co]rc~2cH2ocH2cH2[o~cH2)5~roH
wherein the variable r is sn integer the 8um of r + r has sn average value of 3.7 and the ~verage lecular weight is 527. The structure ~f compound No. 20 is:

~O~(CH )5~0~ (c3H6o)~ ~3H6[0~(CH2)5]r 1~ wherein the sum of r ~ r has an average value of 6 and the average lecular weight is 1,684. This ex-planation m~kes explicit ~he structural formulas of com~ounds 1 to 34 set forth above.
The concentration of the modified ester diol alkoxylate derivatives of the types represented by for-~ulæ I~I, IV, IV A, V and V A in the formulated com~o-s~tions can be from 20 to 80 weight percent, preferably from 25 to 50 weight percen~.

The coating compositions can also contain an organic ~olvent and a catalyst as optional components. Any of the conventional solvents used in the coatings industry can be used at a concentration preferably below 30 weight-percent of the total weight of the coating composition.
While larger ~mounts could conceivably be used, the use of larger amounts would destroy the hi~h solids na~ure ~f the coat~ng, ~olve~t.s are generally added in the small a unts 20.

~ 7 11855-C-l indicated to improve flowability during application of the coating com~osition to the substrate.
In some instance an acid catalyst might be desire~
to improve the efficiency of the melamine crosslinking reaction during curing. The concentration of the cat-alyst can vary from zero eo about 10 we,ght percent based on the total ~eight of the coating composition.
The particular catalyst used ~nd its concentration are dep~ndent to a degree upon its catalytic activity and the ~ specific components present in the coatings composition.
Ihese catalysts are known to those skilled in the art and include hydrochloric acid, sulfuric acid, p-tolLene sulfonic acid, dodecylbenzene sulfonic acid, phosphosic acid and its alkyl derivatives, m2leic acid, trimel-litic acid, phthalic acid, succinic acid, and the like.
The coatin~s compositions can also contain pigments, fillers and other additives conventionally present in coatings compositio~s in their conventional quantities.

The particular ones selec~ed are of no consequence to ~he basic invention. In preparing the coatings compositions, the ingredients are mixed by the conventional procedures uset in the production of paints, inks or coatings compo-sitlons. These procedures are so well known to those skilled in the art that they do not require further dis-cus~ion here.
The coatings compositions are applied to a surface 21.

~ 07 11855-C-l or substrate by conve~tional means and then thermally cured by heating at a temperature ~f about 125 to 250C, preferably from 150 to 200C, for a period of time suf-ficient to obtain a d~ film. Generally, this time will ran~e from about one tc 30 minutes, preferably from 10 to 20 minutes. The components present in a particula- hig~
solids coating c~mposition will determine the temperature and time that will be required to obtain an adequate cure and 2 good film coating.
The coatings compositions of this inventio~ are high solids coatings compositions and they can contain as much as 90 weight percent or more solids therein. Generally the total solids content of the coatings compositions of this invention range from about 70 to 90 weight percent of the total ~eight of the coating composition.
Modified Latex C~mpositions It has also been found that the mDdified ester diol alkoxylate derivatives of the types represented by formulas III, IV, IV A, V and V A can be added to lat~x compositions to ~mprove the properties of the latexes;

in particular ~crylic latexes.
m e latexes that can be used are known to those skilled in the srt and include acrylic acid and meth-acrylic acid derived latexes 8S well as those latexes derived from their esters. m ese latexes are commerci~llv available and are known to be copolymers of two or m~re 22.

l~Z~)7 11855-C-l monomers such ~s methyl methacrylate, styrene, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, butyl methacrylate, methacrylic acid, acrylic acid, 2-hydroxyethyl acrylate, ~inyl chlorite, vinyl acetate, acrylamide, 2-hydroxypropyl acrylate, iso-butoxymethyl acrylamide, maleic acid, glycidyl acrylate, vinylidene chloride, vinyl ethyl ether, butadiene, acrylonitrile, diethyl maleate, vinyi ethyl ketone, and t~e like. Illustrative of copolymer latexes are vinyl chloride/vinylacetate/methacrylic acid, stryene/ethyl acrylate/methacrylic acid, methyl acrylate/styrene/
vinyl acetate/methacrylic acid, and any other known latex.
The a unt of said modified ester diol alkoxylate deriva~ive that can be added to the latex can vary from about 5 to about 50 weight percent, based on th~ total solids content of the latex, preferably from 10 to 20 weight percent. It is added to the latex and stirred in by conventional means to obtain uniform distribution therein. The latex formulation can also contain other components generally present in latex coating compositions such a~, surfactants, antifoams, bactericides, mildewicides, other coalescing acids, freeze-thaw additives, light stabilizers, and the like. These are well known to those skilled in the art, as are ~he amounts thereof required in l~tex coatings, and do not need extensive description or discussion herei~ _o enable one skilled ~ 7 11855-C-l in the art t3 understand their use.
The latex c~atin~ compositions are applied to a substrate by the known conventional methods. They are cured by heating at a temperatu-e of a~out 125~ to 250C, preferably from 150 to 200~C. for a period of time sufficient to obtain a dry fi~m. Generally, this time will range from about one to 30 minutes, preferably from 10 to 20 minutes. The components present in a particular iatex coatin~ composition used will determine the tempera-~ure and time that will be required to obtain an ade-quate cure and a good film coating.
In the following exa~ples the products were evalu-~ted according to the following procedures.
Crosshatch adhes _n refers to a test using 10 paral-lel, single-edge, razor blades to scribe test fiims with sets of perpendicular lines in a crosshatch pattern.
Ratings are based on the amount of film removed after applying and subsequently pulling a contact adhesive tape (Scotch Brand 606) away from the surface of a scribed 20 coating at a 90 degree angle in a fast, rapid movement.

It is Lmportant to carefully apply and press the tape to the scribed co~ting to eliminate sir bubbles and provide a good bond because adhesion is repor~ed as the percent ~f film remaining on the substrate with a 100 percent rat-ing indicating complete adhesion of the film in the sub-~trate.
_ol~ent resistance is a measure of ~he resis~ance of 24.

11855 -C-l the cured fil~ to attack bv solvents, usually acetone or ~ethvl ethvl ~etone, and is reported in the nu~be-of double rubs or cvcles of sol~ent soaked cheese clo.~.
required to remove one-half of a fil~ from che test area.
The test is perfor~ed bv strokin~ the film with an acetone ssturated cheese cloth until that amount of f il~
coating is re~oved. The nu~ber of cycles required to remove this amount of coating is a neasure of the coa~-ing solvent resistance. Values ~reater than 100 are reported as 100 which ~eans less ~han one-half the fil~
was removed after 10~ double rubs.
Reverse impact resistance ~easures the ability of a given fil~ to resist rupture from a falling weight.
A ~,ardner Im~act Tester usin~ an eig~-pound dart is used to test the films cast and cured on the steel panel.
The dart is raised ~o a given height in inches and drop-ped onto the re~erse side of a coated ~etal panel. The inches ti~es pounds, desi~nated inch-pounds, absorbed bY
the fil~ without rupturing is recordet as the reverse im-pact resistance of the film.
In this application, the following definitions define certain co~pounds that are used in the exanples:
Silicone Sur actant I is r ~H3- -CH3 (CH3)3SiO r SiO- _ -SiO L Si(CH3)3 L CH3_ 13 ~3H6(0C2~I4)70H
Epoxide A is 3,4-epoxycyclohexvlmethyl-3,4-epoxycyclohexane car~oxylate~

25.

11855 -C-l The f~llo-iing experiments show the production of ester di~l ~lkoxylates II.
Preparation Of Ester Diol Alkoxvlates II
- Experiment A
-A reactor ~as charged with 408 grams of freshly stripped solid 2,2-dimethyl-3~hydroxypropyl 2,2-dim- -ethyl-3-hydroxypropionate ~nd 1.39 grams of potassium metal as cat~lyst and heatet to liquify the solid. The reactor was purged with nitr~gen and then over ~ lO hours addition period 528 grams of ethylene oxide were added while maintaining a temperature of from 106 to 114C.
After all of ~he ethylene oxide had been added, the re-action was continued at 114C. for 30 minutes 'co com-pletion. The reaction produc~ was neutralized with 1.69 grEms of acetic ~cid and vacuum stripped at 60C. and 1 mm of Hg pressure. The liquid ester diol ethoxylat~
secovered weighed 922 grams as the residue product con-taining a mi~or amount of by-products.
The ester diol alkoxylate produced had an average of about 3ix (~ + y of Formula II) ethyleneoxy units in the m~lecule. m e average molecular wei~.t was 480, the Brookfield viscosity W2S 194 CpS. at 26C. ~No. 3 spindle, 100 rpm.)~ the specific gravity was 1.079 g/cc and the Gardner color was less ~han 2. Ihe water dilutability was 250. Water dilulability defines the gram~ of water that c~n be ~dded to lO0 gra~ of the ester diol ~lkoxylate to achieve a haze point.
~ 6.

11855-C-l llfl~ {)7 Exper~ent B
Following the proredure similar to that described in E~periment A, 792 grams of ethylene oxide and 612 grams of 2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3-hytroxy-~ propionate were reacted using 2.1 grams of potassium catalyst. The ethylene oxide feed time was about 11 hours.
The liquid ester diol ethoxylate residue productproduced wPighed 1,391 grams; it had an aver~ge of a~out six ethyleneoxy units in the molecule. The average molecular weight was 477, the Brookfield viscosity was 200 cps. at 24.5C (No. 3 spindle, 100 rpm), the specific gravity was 1.08 g/cc and the Pt/Co color was 60 Water dilutability was 296.
Ex~eriment C
Following the procedure similar to that described in Experiment A,528 grams of ethylene oxide and 612 grams of 2,2-dimethyl-3-hydrsxypropyl 2,2-dLmethyl-3-hydroxy-propi~nate were reacted using 1 gram of potassium as cat~lyst. The ethylene oxide feed time was about 9 hours.
The liquid esterdiol ethoxylate residue produc~ pro-duced weighed 1,128 grams; it has an average of about four ethyleneoxy unies in the molecule. The average molecular weight was 392, the Brookfield ViscGsity was 168 cps. at 27C ~o. 3 spindle, 100 rpm), the specific 27.

ll~Z~7 11855 -C-l gr~vity ~as 1.07 g/cc and the Pt/Co col~r was 40. Water dilutability was 200.
Experiment D
Foliowing the procedure similar to that described ~n Experiment A 220 grams of ethylene oxide ~nd 510 gr~ms of 2,2-dimethyl-3-hydroxypropyl 2,2-dimRthyl-3-hydroxypro-pionate were reacted using 1.1 grams of potassium ~s cat-alyst. me ethylene oxide feed time was a~out S hours.
The liquid ester diol ethoxylate residue product produced weighed 730 grams; it had an average of about two ethyleneoxvunits in the molecule. The average mDlecular weight was 2g5, the Brookfield viscosity was 285 cps at 25C. (No. 3 spindle, 100 rpm) and the Pt/Co color was 75. Water dilutability was 86.

~=~
A stainless steel autoclave was charged with 3,011 grams of solid 2,2-dimethyl-3-hydroxypropyl Z,2-dimethyl-3-hydroxypropionate ~nd 18 grams of boron trifluoride etherate and the contents were heated to 60C. Then the autoclave was pressured to 10 psi with nitrogen and the ethylene oxide feed was searted. A total of 2,604 grams of ethylene oxide was added over a period of about six hours while maintaining the reactor ~emperature of 65 to 68C. and the pressure between 1~ and 30 psi. After all the ethylene o~ide had been ~dded the temperature was maintained at 65UC. until no ethylene oxide pressure remained in the reactor. The product was cooled to 40C; 2 weight percent of magnesium sili~ate neutralizing agent was 28.

11855 ~-1 ~ 0 7 added and the mixture was stirred at 40C. for one hour. The temperature was raised to 90C. and held while a vacuum was applied to remove vol~tile products.
This vacuum was continued until the pressure in the reactor reached 5 mm. of mercury. The clear/colorless product was pressure filtered to rem~ve insolubles.
m ere was recovered 5,494 grams of the li~uid ester diol ethoxylate residue product having an average of about four ethyleneoxy units in the molecule. Ihe average mole-cular weight was 382, the Cannon Fenske viscosity was 90 cks at 100F. ~nd the Pt/Co color was 30; it had anacid value of 0.06 percent as acetic acid. Gas chro~Ato-graphic analysis indicated that the product was free of neopentyl glycol ~nd its ~dducts.
In a similar manner the mixed ester diol ethoxylate/
propo~ylate is produced using a mixture of ethylene oxide and propylene ~ide as the feed ~tPrial. Likewise, the ethoxylatelstyroxylate is produced.
Experiment F
~ Following a procedure similar to that described in Experiment A, 204 grams of 2,2 dimethyl-3-hydroxypropyl 2,2^dimethyl-3-hydroxypropionate and 440 Rrams of e~hylene oxide were reacted at 99~ to 115C. using 1.5 grams of bor~n trifluoride etherate ~s the catalyst. The ethylene oxide feed time w~s about 4.5 hours and the mixture was 29.

11855~-1 heated an ~dditi~nal 0.75 hours after co~pletion of the addition. Then 13 grams of magnesium silicate were added and the mixture was stirred overnight At 50 to 65C. It was filtered, then stripped at 100C. for one hour to a pressure of 5mm. Hg.
The liquid ester diol ethoxylate residue product produced weighed 602.4 ~rams; it had an average o~ nbout 10 eehyleneoxy units in the molecule. The Brookfield viscosity was 193 cps at 30C. (No. 3 spindle, 100 rpn) the specific gravity was i.046 g/ec and the Gardner color was 1.5. Water dilu~ability was 15.6 ExPeriment G
Following the procedure described in Experiment F, 204 grams of 2,2-dimethyl-3-hydroxypropyl 2,2-dim-ethyl-3-hydroxypropionate was reacted with 440 grams of ethylene oxide using 1.5 ~rams of boron trifluo~ide ether-ate as the catalyst. The ethylene oxide addition time was about 7.5 hours.
The liquid ester diol etho~ylate residue product 2~ produced weighed about 629 grams after filtering and stripping. It had an average of about 10 ethyleneoxy units in the molecule. The Cannon FenSke viscosity at 100F was 103.4 cks., the specific viscosity was 1.046 g/cc and the Gardner color was 1. Water dilutability ~as 15.4 Experiment P.
Following the procedure described in Expesimen~ F, 30.

il'~Z~)7 11855 -C-l 125 ~r~s of 2,2-dimethyl 3-hydroxypr~pyl 2-2dimethyl-3-hydroxypropionate was reacted at 48 to 132C with a total ~f 502 ~rams of ethylene oxide using a total of 1.3 grams of potassium as the catalyst. The ethylene oxide feed time was about 9.5 hours. At the completion of the feed 11.9 grams of ma~nesium silicate were added and the mixture was stirred for one hour and then cooled.
Ihe ester diol ethoxylste was filtered hot and stripped under vacuum.

The stripped ester diol ethoxylate residue product recovered weighed about 585.3 grams. It had an average of ~bout 19 ethyleneoxy units in the molecule. The Cannon Fenske viscosity was 115.5 cks at 100F. On standing it solidified at 25C. and melted at about 27C.
ExPeriment I
In a manner similar to that described in Experiment A, 805 grams of 2,2-dimethyl-3-hydroxypropyl 2,2~dimethyl-3-hydro~ypropionate and 8 grams of boron trifluoride etherate were melted at 60C in a reaction flask. Over a period of about 1.75 hours a total 811 grams of pro-pylene oxide were added at a temperature of 57 to 60C.
The reaction mixture was stirred about another 2 hours;

32.3 grams of magnesium silicate were added and stirred at about 70C for about 1.5 hours. It was then stripped at 70~C for 0.5 hours at 4-5 mm. of mercury and filtered.
The liquid ester diol propoxylate residue product was 31.-~ 7 11~55 -C-l clear ~nd c41Orless and w~ighed 1,50~ grams. It had an average of qbout 4 propyl~eo~ units in the m~lecule.
Ihe following examples serve to further define this invention; psrts are by weight unless otherwise indicated.
Pre~aration Df Anhydride Modified Ester Diol Alkoxvlates III And Formulations Thereof ExamPle_ 1 Part A - A glass-lined autoclave was charged with 429.47 par~s of 2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl -3-hydroxypropionate ~nd 2.4 parts of boron trifluoride etherate. The mixture was heated to 55C and 370.5 parts of ethylene oxide were added over a period of about 13 hours. This mixture was then held at this temperature for four more hours. Then, 2 percent by weight of mag-nesium silicate was added and the contents were heated to 90C and stirred for 4 hours. Thereafter the pressure was reduced to 20 mm Hg and the,product was stripped for four hours to re ve volatiles. AtmDspheric pressure was re-stored with nitrogen, the contents were cooled to 50C, and transferred to a storage autoclave. Five parts of filter~id were added, ~he contents were m~xed for 30 minutes, and then filtered and stored. A second batch was made in the sæme manner and both batches were bl~nded by plac-ing the materials in a large autoclave, heating the con-tents to 90C, and stripping the pr~duct 4 hours at 5 mm Hg. There ~as obtained a large quantity of the liquid ester diol ethoxylate havillg an average of about 4 ethylene-oxy units ~n the lecule.

32 .

1185~ C-l Part B - A 236.7 ~rams p~rtion of the above liquid ester diol eth~xylate (Part A) was charged to a re-~ctor together with 163.3 gr~s ~f phthalic anhydride and 96 grams of 2-ethoxyethyl acetate as the solvent.
The ~i2ture was stirred and heated at 140C for 30 minutes. The anhydride modified ester diol ethoxylate III had the following average structural formule:

COOH COOH
~CO(O C2H4~xCH2C CH200C C Q20(C2H40)yOc~

~n whieh the sun ~f x and v have an average ~alue of about 4.
The mixture ~lso contained unreacted ester diol ethoxvlate It had a Brookfield viscosity of 386 cps at 25C and an ~cid number of 124 mgm. KOH/gm.
?art C ~ A coatiLng ~om~osition was prepared by mixing 10 grams of the above anhydride modified ester diol etho~ylate (Part B), 10 grams of hexamethoxymethylmela-mine, 0.5 gram of N,N-dimethylethanolamine, 3 grams of distilled water, and 0.05 gram of Silicone Surfactant I.
Films were prep~red by casting the above composition on steel pannels wi~h a No. 40 w~re-wound rod and thermally curing in a circulating 2ir oven. Curing for 20 minutes at 220F afforded no cure. Curing for 20 minutes at 250F

produced films with a 4B pencil hardness, 43 acetone rubs, 6nd greater than 320 inch-pounds reserve im~act resistance.
In this compo~ition, cure was achieved even in the ab-sence of catalyst.

ll;~Z~07 11855-C-l E~am~le 2 - A coating com~osltion was prepared by mixing 10 grams of the ~nhydride mDdified ester diol alko~y~ate (Psrt B) of ~xample 1, 10 grams of hexamethoxymethylme-lsmine ~s crosslinker, 0.5 gram of N,N-dimethylethanola-- mine, 3 grams of distilled w ter, Q.05 gram of Silicone Surf~ctant I, ~nt 0.2 gram of a 40 percent solution of p-toluenesulfonic acid dissolved in ~n organic solvent as the catalyst. Cured fi~ms were prepared as described ~n Example 1, Part C. ~uring for 20 minutes at 220F
afforded fiLms with 100 acetone ru~s, F pencil hardness, and hi~h reverse i~act resistance. A film cured at 250F for 20 minutes achieved a 2H pencil hardness, 100 acetone rubs, and high reverse lmpact resistance. The im~roved properties obtained by the use of a cure cat-alyst are clearly evident.
E~ample 3 - A s~eries of high solids ~oating compositions was produced by mixing 10 g~ams of the anhydride modifi-ed ester diol ethoxylate ~Part B) of Exam~le 1, Ep~xide A, stannous octoAte catalyst, 0.1 gram of Silicone Surfact~nt I, and 1 gram of xylene. Film3 were prepared from the 8S weight percent solids solution as described in Example 1 Part C. Curing at 200F for 20 minutes produce~ clear dry films. m e quantities o~ reactants used and proper-ties of the cured films are tabulated below; all ~he films were sm~othwith high gloss.

34.

11855-C-l Experime~ts Formulation A B C D

Example 1, Part B 10.0 10.010.0 10.0 Product, g - Epoxide A, g 15.0 10.0 7.5 6.0 Stannous Octoate, g O.23 0.180.15 0.14 CoatinR Properties Reverse Impact 5 250 ~ 320 300 ~n-l~s.

Acetone Ru~s 100 100 92 68 Pencil Hardness H 2H 2H . 2H
______ _____________ For~ulat~nB represents the optimum therEDset characteris-tics. The C and D formulation5describe the decrease in thermoset characteristic~ that occur when the amount of epoxide is decreased and the re~ultant high impact snd hardness that ~ achieved at the cure conditions used.
FormulationA is a hard coating with e~cellent ~hermoset 2~ characteristics-E~amPle 4 - A pigmented high ~olids coating composition was produced by blending 100 græms of the anhytride modi-fied ester diol ethoxylate of E~ample 1, 180 grams of titanium dio~ide pigm~nt, 3 grams of stannous octoate cat-slyst, 1 gram of Silicon~ Surf~c~ant I, ~nd 40 grgms of xyl~ne In 8 ball m~ vernight. Subsequently, 61.73 grams of Epoxide A ~nd 30 græms of xylene was mixed with 200 grams of the above mixture to afford a 77 ~ight percent solids co~ti~g compositlon with ~ Br30kfield viscosity of 180 35.

~ 11855-C-l centipoises at 25C. FiL~s pre?ared according to the procedure descr~bed in Example 1 were c~red at 220F
for 20 minutes. The fiLm produced passed 100 acetone rubs, had high gloss, had excellent adhesion an~ achie-ved a pencil h~rdness of 2H.
~ ExamPle 5 Part A - A 360 grams portion of ~he liquid ester diol ethoxylate of Part A of Example 1 was reacted with 40 grsmc of phthalic anhydride for 30 minutes at 140C
1~ ~O produce ~ phthalic modified ester diol eehoxylate having a Brookfield viscosity of 500 cps and an acid ~u~er of 40 mgm. KOH/gm.
In ~ similar manner succinic anhydride can replace phthalic anhydride.
Part B - A coating com~osition was produced by ~ xing 100 grams of the above product of Part A with 100 grams of hexamethoxymethylmelam~ne, 140 grEms of titanium di-o~ite, and 25 gr~m~ of 2-ethoxyethyl acetate. The mix-ture was mixed overnight in a ball mill. Then a 158.5-gram portion was separated and mixed with 1 gram of phos-phoric acid catalyst and 25 fldditionsl grams of 2-ethoxy-ethyl acet~te. Films prepared by the procedure described in Example 1 were cured for 20 minutes at 300F. The film had good solvent resista~ce (m~re than 100 acetone rubs), good adhesi3n, ~nd 75 inch-pounds reverse impact resistance.

36.

7 11855-C-l l e 6 Part A - A 320 ~rams portion of the liquid ester diol eth~xylate of Par~ A of Ex~aple 1 was reacted wlth 80 grams of phthalic anhydride for 30 minutes at 140C
to produce 8 phthalic modified ester diol ethoxyLate ~ having ~ Brookfield viscosity of 1,690 cps and an acid num~er of 77 m~m. ROH/gm.
Part B - A co~ting composit~ was produced by charging 100 grams of the product ~f Part A, 100 grams of hexa-methoxymethylmelamine, 140 grams of titanium dioxideS
and 30 grams of 2-ethoxythyl acetate to a ball ~ill and rolling it overnight. Then a 163.5-~ram po-tion of the mixture was blented with 1.5 grams of phosphoric acid, 0.42 gram of Tinuvin 770 ~ (a W stabilizer marketed ~y Ciba-Geigy), 0.11 gram of Irganox 1010 ~ (a branched phenol antioxidant marketed by Ciba-Geigy), 50 grams of 2-e~hoxyethyl 2cetate, and 4.55 grams of a polycapro-lactone triol having an average molecular weight of 300 and sn average hydroxyl number of 56~. Films were pre-pared accor~ing to the procedure described in Example 1 and cured for 20 minutes at 250F. The film produced was solvent re.qist~nt (more than 100 ace~one rubs~, had a pencil hardness of 2B, and passed 50 inch-pounds reverse im~act resistance.
Exam~le 7 Part A - A 280 gr~ms portion of the liquid ester diol ethoxylat? of Part A of Example 1 was reacted wi~h 120 ~ 07 1185~

~rams of phthalic anhydride for 30 minutes at 140C.
to produce a phehalic ~Ddified ester diol echoxylate having a Br~okfield viscosity of 18,280 cps and an ac~d number of 115 m2m. KOH/gm.
Part B - A costing composition w~s produced by charg-~ ing 1~0 grams o~ the product of Part A, 100 grams of hexamethoxymethylmelamine, 140 grams of titanium di-oxide, and 40 grams of 2-ethoxyethyl acetate to a ball mill and roll~ng the mixture overnight. Then a 173 gram portion of the mixture was blended with 1.5 grams of phosphoric ~cid, 40 grams of 2-ethoxyethyl acetate, ~nd 4.5 grams of the polycaprolactone triol used in Exam~le 6, Part B. A film was prepared according to theprocedure described in Exam~le 1 and cured ~or 20 minutes at 259F. ~he film produced was solvent re-~istant ~ore than 100 acetone rubs) and h~d a re-verse impzct resistance of 200 inch-pounds.
Pre~aration Of IsocYanate M~dified Ester Diol Alkox~lates IV And IV A And Formulations Thereof ExamPle 8 Part A - A series of iso~y~nate m~dified ester diol e~hoxylates was psepared by reacting the ester diol ethoxylate of Part A of Example 1 with 3-isocyanato-methyl-3,5,5-tr~methylcyclohe~ylisocyanate (IPDI) 8~
45C for about ~ hours. The resulting pro~uc~s con-tained unreacted ester diol etho~ylate and i~s hydro~yl ~z~07 11855 -C-l terminated diureth~ne dervative. The quantities re-acted and properties of the product mixtures produced are ta~ulated below:
Run (1) (2~ (3) (4) Exam~le 1, Part A, g! 95 90 80 85 IPDI, g 5 10 20 15 Stannous octoate, g 0.1 0.1 0.1 . O.1 Product ProPerties Brookfield viscosity, 512 1,588 33,000 6,000 cps at 25C

Water dilutability, gms.
water/100 ~ms. prDduct to h~ze point. 1~6 78 21 Part B - Aqueous co~ting compostions were formulated and cur d following the procedures described in Exam~le 1, Part C. The data are summ~rized in the following table:

39 .

11;~26{)7 11~55~

~ ~' g _ o ~
_ _ ~ ~ _ -- O r~ o -- O , U2 _ _ _ C
~ ~ 8 s ~ _ .
_ ~ o ._ L
l O ~ o ~ g g ,Q ~ O
~1 ~ ~ o ~ ~ -- ~

_ O ".~ - 3 ~ ~ o 1~
. ~ . , ~ ~ ~ 8~ g Y o , ~ `.
, , ~ o _ C) o~ ", o = "~, C
~ ~ ~ F
O o -- O o O ~ ~1 ~ , o ~ o ~

, ~n 0, ~ ~
o , ~ o O O ~ 0 ~ g 2: 0 ' E
~ ~ -- ~ o ~, _ ,,' _ 8 ~
~., .,. _ o ~ ., o o o ~ 8 2 g C

F, ~ ' U:
~ ~ ~ .

a ,~ e c ~ b o ~ ~ 0 ~ o e ~ ~ c _ , u C _ - - ~ 3 6 ~ 1~ ~ t I~
Ei El ~; ~ o ~ ~
O b " ~ X '~ O ~ CJ
1~. ~ ce ~ 3 ~ *

40.

Z~7 11855 {~-1 _ o '^ 0 o o _ c ~ o ~ ~ C ~ U, _ . c _ ~
~ , , o o . -- 8 r~ 2 - ~ C
_ ~ ~ C ~ ~
~' _ a o ~ o = 3 ~ ~
o o ~ o ~ o _ a~ C ~ o ~
c _ ~q UO~V~ oO
, o I o ~ o 8 g -- ol o~ , , ~ , _ ~ ~ o O ~ o r, ~ o o s o o ~ o ~ o 0 ~ 2 ~ 5 c = E
_ , i_ u~ u. O = o c . ~
, , ~ , o o. ~ ~ ~ o ~ ' u ,~ .o ~ ~ o ~ ~ _ w _ .
_ _ CJ
-o:

. ' E o ~ ~ C
, ~ ~ ~ _ 8 ' ~ c ., ~ , , I ~ ~
~ C ,, ~ ., 1~ t~ " C ~ _~

~ O a ~ u _~ ~ ~ Q O O L Q. 1~. ~ 90 -- c o I V ~ ~ C IU t c ~ C
O _ .~C) ^
E E E ~ ~ o ~ U ~ ' ~,~
O. 3 tl~ ~ V ~ `3 41.

11;ZA; ~37 118S5-C-1 E~c a~F 1 e Part A - A 160 gr~q portion of the ester diol ethoxylate of Part A of Example 1 was reacted with 40 grams of IPDI
for 2 hour~ at about 50C in contact with 0.2 gram of stannous octoate as catalyst to produce a mi~ture con-tai3 ~ g ~re2cted ester dlol eeho~cylate asld its hydro~yl _ terminated diurethane derivative.
~art B - To the above reaction mi~ture there were added 35.3 grams of phthslic anhydride ~nd 58.8 grams of 2-ethoxy-0 eth~l acetate. The ~ture w~S heated for 30 minu~es140C. to pr~duce ehe phthalic anhydride partially capped reacti~n product mi Yture.
Part C - A seri~s of CoAt~ng com~ositlons was prepared and cured by the procedures described in E~ample 1. Coatings 1 to 4 were cured for 20 minutes at 350~F; coat~ng 5 was cured at 250F. TSe com~osition ~nd properties are tab-ulated below:
I:oatin~ 1 2 3 4 5 Fo~aulation. Pllrts 2~ Exam~le 9, Part B 8 10 12 10 10 ~e~amethoxy~ethyl- 12 10 8 ld 10 meLamiD.e Sil~co~e Surfaetant I 0.1 0.1 0.1 0.1 0.1 p-Tolue~esulfo~ic acid 0 0 0 1.25 1.25 Ethoxyethyl Acetate 2.0 2.0 2.0 2.0 2.0 Coatin~ ProPertie~
Reverse Im~act, in-lbs. 300 300 300 5 15 Acetane R~bs 14 lO0 100 100 100 Pencil Hartne3~ 4B H~3 HB 5H 3H
3D Adhesion, Z 100 100 100 100 lOU
42.

11855~-1 Preparati~n of Epo~ide M~d~fied Ester Diol Part A - A 348 grams portion of the liquid e~er diol etho~olate of Part A of E~ample 1, 52 gram~ of Epo~ide A
and 1.2 gra~ of stannous octoate (added in two portio~s) were reacted at 150C for 10 hours. The epoxide dified ester diol etho~olate produced e~ntained 0.~8 weight per-cent unreacted Epo~ide A in the mixture.
P~rt ~ - A serie~ of aqueous coating eampostion was pro-duced 3nd cured following the procedures described in Ex-nmple 1. m e tata are summarized in the following table:

Coatin~ 1 2 3 4 Formulation~ ~arts E~ample 10 Part A 8.0 10.0 12.0 14.0 Hexamethoxymethylmel ~mi ne 12.O 10.0 8.0 6.0 p-Tolu~ne~ulfonic acid 1.0 1.0- 1.0 1.O
Dlst~lled Water 2.0' 2.0 2.0 2.0 Silicone Surfactant I 0.1 0.1 0.1 0.1 ture Tamp... ~F 20 250 20 250 20 250 200 250 Coatin~ ProPerties Reverse Impact~ in-lbs. 5 ~5 ~ 5 5 25 ~5 50 25 Acet~ne Rubs 10 100 10 100 10 100 100 100 Pencll Hardness 5~ 5~ 4H 5H ZH 5H F H

The results ~ndicate that hard, thermoset coatings were prepared.

ExamPle 11 Part A - A mi~ture of 300 grams of the epoxide mDdified ester diol ethoxal~te of Part A of Example 10, 75 grams 43.

Z~7 11855 {:- 1 of phthalic anhydride nnd 94 grams of 2-ethoxyethyl ~cetate w~s hested and reRcted for 30 minutes st 140 C. to produce the phthalic anhydride capped der~vative of the epoxide dified ester diol ethoxylate h~ving a Brookfield vis-- cosity of 500 cps Bt 25 C.
Part B - A coaeing composition was produced by blending 12.5 grams of the capped product of Part A ~bove, 10 grams of hexamethoxymethylmelamine, 0.1 gram of Silicone Surfact-cnt I, and 2 gra of 2-ethoxyethyl acetate. Fi~ms prepared according to the procedure described in ExamPle 1 were cured for 20 minutes Rt 350F. The cured fi~ms obtaine~
~chieved a B pencil hardness, iO0 acetone rubs, and 320 inch-pounds of reverse impact resistance.
PreParation of Miscellaneous Fromu~tions Usine Polyol And Latexes ExamPle 12 A eries of C08ting compositions was protuced using various anhydride modified ester diol ethoxyla~es produced supra in coniunction with 8 low molecular weight polyol. The formulations and their coating properties are tabulated below; all coatings were cured for 20 min-utes ~t 25D~F.

4~.

~ ~ 11855-C-l Coati.n~ 1 2 3 4 5 6 Formulation, parts . _ E~ample 5, Part A Adduct 8.5 7.0 0 0 0 0 Example 6, Part A Adduct 0 0 8.5 7.0 0 0 _ Exam~le 7, Yart A Adduct 0 0 0 0 8.5 7.0 Trimethylolpropane (~) 1.5 3.0 1.5 3.0 1.5 3.0 ~exametho~ymethylmelamine lO lO lO lO 10 lO
Phosphoric Ac~d 0.2 0.2 0.2 0.2 0.2 0.2 Sili~one Surfactant 1 0.1 0.1 0.1 0.1 0.~ 0.1 Etho~yethyl Acetate 2.0 2.0 2.0 2.0 3.0 3.0 Coating Properties Reverse Impact, ~n-lbs. 100 ~5 25 ~5 75 C5 Acetone Rubs lQ0 lO0 100 100 lO0 100 Pencil Hardness 3H SH 3H ~H 3H 6H
A & esion, % lO0 100 100 100 100 100 All fi~s were clear,smDoth, glossy9 and therm~set in charac-ter. A & esion ~as e~cellent. The formul~tions containing the large amount of TMP were ver~ hard and as a result had ~inimal ~mpact resistance.
E~am~le 13 C02ting com~os~tions were produced si~ilar to those described in Example 12 ~ut containing higher con-centrat~ons of the Adducts s~d decreased trimethylolpropane concentr~tions. The coatings ~ere cured at 250~F for 20 mi~utes. The results are tabulated belo~.

45.

Zti~)7 11855~-1 Coatin~ 1 2 3 4 5 6 7 8 Formul~tion. Parts Example 5, Part A Adduct 9,0 9.5 0 0 O 0 0 O

Ex2m~1e 6~ Part A Adduct 0 0 9.0 9~5 9 9 0 0 - Example 7, Part A Adduct 0 0 0 0 0 0 9.5 9.O

Trimethylolpropane 1.0 0.5 1.0 0.5 1.0 1.0 1.0 0.5 ~examethoxymethylmel~mine 10 10 10 10 6.7 15 10 10 Phosphoric ac~d 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silicone Surfact~nt I 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Ethoxyethyl Acetate 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Coatin~ Properties Reverse Impact, in-lbs. 25 50 50 25 25 25 50 75 Acetone '~ubs < - lOC

Pencil Hardness 2H 2H2H 2H 3H H 3H 2H

Adhesion, % ~ 100 -Thus good overall coating properties were obtained in all inst~nces. Adhesion was excellent.
~L
A pigmented composition was produced by mixing 90 grams of the prodl~ct of Part A of Example 6, 100 grams o~ hexamethoxymethylmelamine, 10 grams of the polycapro-lactone triol used ln Part B of E~am~le 6, 140 grams of titanium dio~ide, and 40 grams of 2-e~ho~yethyl acetate and r~lling overnight in a ball mill. A l9-gram portion of the ~Di~ture was blended with 0.2 gram of stannous chloride End 1 gram of 2-ethoxyethyl acetate to produce 46.

11855 -C-l pigmented c~ating compositi~n. A fil~ ~as prepared ~c-c~rding to the procedure described in ~am~le 1 and cured for 20 minute.c st 200~F. The film pr~duced was solvent resist~nt (more than 100 acetone rubs), impact resistan ( re than 320 inch-pounds), and had a 8 pencil hardness.
- amPle 15 -A ~eries of coat~ng c~mposlti~ns waQ pro~uced by blending a Qtyrene/ethyl ~crylate/methacrylic acit/

2-hydroxyethyl ~cryl2te Latex compositlon having a total ~olids of 43 weight percent with the product of Part A .

of E~a~ple 6. The aqueous Late~ was dified to imprsve its fil~-fonming properties a~d to establish that the ~hydride dified ester diol ~lko~ylates ace as a resctive coalescing ~id. The f~r~lations were produced by mi~ing the co~onent~ described i~ the followLng table at room temperature. The pr~duct of Part A of E~ample 6 was ti-luted t~ 50 weight percent solids with ~istilled water a~d neutralized to a pH of 7.4 with N,N-dimeehyleeh2nolamine.

Run 1 2 3 4 5 6 7 ComPosition~ solid Late~c, gms. 10 1~ 10 10 10 10 10 Eacample 6, Part A adduct, gms. 0 0.~ 1.0 1.5 0.5 1.0 0.5 ~ex m~thoxyme~hylmelamine O O O 0 0.5 0.5 1.0 Water 13 . 3 13 . 8 14. 3 14 . 8 -13 . 8 14 . 3 13 . 8 F~lms were cast on Bonderite No. 37 s~eel panels with a No. 60 wi~e-wound rod ~nd allowed to stand under amoient condition3 overs~ight. ~e ilms were than observed for ap-pearance and placed in an ov~ for 20 m~nutes at 350 F. The results are reported ~n the follos~in~ t2ble:

)7 11855 -C-l Run l 2 3 4 5 6 7 Film ProPerties Appearance prior to (1) (l) (2) (3) (4) (3) (3) curi~g - Appearance after (l) (1) (2) (3) (4) (3) (3) cure Acetone rubs, cycles No cure 60 100 lOO lOO 100 100 Reverse impact, in-lbs. No cure ~3 15 300 ~5 5 4H
~encil hardness No cure ~ F 2B H H 300 ___________________O___ (13 Heavy mud cracking (2) Moderate m~d cracklng (3) Smooth (4) Trace of mut cracking Example 16 Part A - A reactor equipped with a stirrer, condenser, nitrogen inlet tube and ther~ometer was charged with 100 parts of the ester diol propoxylate of Experinent I and 59 parts o~ phthalic anhydride. The mixture was then hea~ed to 140C and stirred at this te~perature for 90 ~inutes.
~he anhydride ~odified ester diol propoxvlate adduct was clear, ~iscous and had an acid num~er of 138 mg~. of KOH/gm.
A 5 gram portion diluted with 15 grams of 2-ethoxyethyl acetate had a Brookfield viscosity of 460 cps at 27~C (No. 4 spindle, 100 rpm~.
Part B - A series of catalyzed coating co~positions was produced,applied to steel panels using a No~ 40 ~se wound rod and cured. ~he for~ulations con~ained 0~1 gran of Silicone Surfactant I and the following componen~s in gra~s:

48.

11855-C-l ~or~lation A B C D
~art A Adduct 10 10 10 10 Hexamethoxymethylmelamine 4,3 4.8 5.6 0 Epoxide A 0 0 0 10.8 _ - p-ToluenEulfonic Acid 0.05 0.05 0.05 0 Stannous Octoate 0 0 0 0.2 Butyl Acetate 3.1 3.2 3.4 4.9 2-Etho~yethyl Acetate 3.0 3.1 3.3 4.0 Formulations A, B and C were cured at 300~ F
and D at 250F. for 20 minutes. All cured coatings had reverse and front i~pacts greater than 320 in.-lb. and 10D% crosshatch adhesion values. Fsrmulations A, B and C
passed 100 acetone rubs; formulation D, 65 acetone rubs.
The pencil hardness ~alues of formNlations A, C and D were 2H, that of B was H.
Part C - A second series of formulations was prepared identical to Formulations A to D but without the addition of ~ny p toluenesulfonic acid or stannous octoate. These are identified as Formulations E, F, G and H respec~ively.
In addition Formulation I was produced containing 10 parts of the Part A Adduct, 0.1 part of Silicone Surfactant I, 7 parts of but~l acetate, 6.3 parts of 2-ethoxyethyl acetate and 21 parts of bis(3,4-epo~ycyclohexylmethyl) adipate.
The formulations were applied to steel panels as in Par~ B
and cured at 300F for 20 minutes. (Formulations H and I
were also given ~n initial precure of 20 ~inutes at 250F).
All cured coatings had re~erse and front impacts greater than 320 in.-lb. and 100% crosshatch adhesion values.
Formulations G, H and I passed 100 acetone rubs; for~ulation 49.

2ti~7 11855 - C-l E, 50 ~cetone rubs; formulation F, 75 acetone rubs. The pencil hardness values of F, ~ and I were F, that of E was H and that of H was 3H.
EX _E~
A pigment grind was prepared using 100 parts of the anhydride modified ester diol ethoxylate of Example 1, Part B, 180 parts of titaniu~ dioxide, 2 parts of stannous octanoate, 1 part of Silicone Surfactant I, and 4 parts of xylene by grinding in a ball mill.
To 161.5 parts of the pigment grind there were added 28.9 parts of bis(3,4-epoxycyclohexylmethyl) adipate, 20.35 parts of 4,4'-dicyclohexy~methane diisocyanate and 40 parts of xylene and the mixture thoroughly blended to yield a formulation having a ~iscosity of 180 cps at room temperature. Steel panels were spray-coated and cured at 220F and 250F to yield hard, adherent, thermoset coatings with good impact resistance and high gloss.
Example 18 A series of coating formulations was produced containing the indicated eomponents. They were then applied to steel panels using a No. 40 wire-wound rod and cured at 220~F and 250F for 20 minutes to yield hard, adherent, thermoset coatings with generally excellent impact resist~nce. Each formulation contained 10 parts of the anhydride modified ester diol ethoxylate of Example 1, Part B, 0.2 part of stannous octanoate, 0.1 part of Silicone Surfac~ant I and 2 parts of 2-ethoxyethyl acetate in addition to the epoxides identified below.

50.

Z~)7 11855-C-l Epoxide Isocvanate . _ Formulation A B A
.
(a~ 3.74 0 4.07 _ (b) 5.78 4.0i (c) 7.54 0 0.5 (d) Q 11.55 0.5 (e) 11.34 0 0.5 (f) 0 17.3 0 5 Epoxide B - bis(3,4-epoxycyclohexyl-methyl)adipate lD Isocyanate A - 4,4'-dicvclohexvlmethane diisocyanate E~a~ple 19 A formulation was proauced by blending 10 parts of the anhydride m~dified ester diol ethoxylate of Example 1, Part B, 5.78 parts of bis(3,4-epoxycyclohexyl-methvl) adipate, 4.07 parts of 4,4'-dicyclohexylme~hane diisocyanate and 0.2 part of stannous octanoate. ~ne mil coatings were applied to a 0.5 inch ~y 1 inrh portion of two 1 inch wide by 1.5 inches long ~etal strips. The two coated edges were held together wnth a paper clip and cured for 20 minutes at 300F. In tw~ replicate tests, it was found that an avera~e tensile force applied to the two ends of the adhered strips of about 600 pounds was required to break the adhesive bond that had been formed.
Esampl~ 20 A series of adhesive compositions was prepared, ea~h containing 10 parts sf the anhydride ~odified ester diol ethoxylate of Example 1, Part B, and the ~ollowing components:
51.

11855-C-l Adhesive ~ (2) Epo~ide A O 10 Hexamethoxy~ethvlmelamine 10 0 Stannous octoate 0 0.2 p-Toluenesulfonic Acid 0.2 0 Adhesive (1) required an average tensile ~rce of 8.8 pounds to break the bond; an average tensile force of 37.5 was required with Adhes~-ve (2).

52.

Claims (22)

WHAT IS CLAIMED IS:

1. An isocyanate modified ester diol alkoxylate comprising the reaction product of (A) an ester diol alkoxylate of the general formula:

wherein m is an integer having a value of from 2 to 4, n is an integer having a value of from 1 to 5, x and y are integers each having a value of from 1 to 20 and R is an alkyl group having from 1 to 8 carbon atoms; and (B) from 0.025 to 0.9 isocyanato equivalent per hydroxyl equivalent of a polyisocyanate.

2. An isocyanate modified ester diol alkoxylate as claimed in claim 1 , wherein m has a value of 2 to 3, n has a value of 1 to 3, x and y each have values of from 1 to 10 and R is an alkyl group having from 1 to 3 carbon atoms.

3. An isocyanate modified ester diol alkoxylate as claimed in claim 1, wherein n has a value of 1 and R
is a methyl group and wherein the isocyanato is 3-isocyanatomethyl-3,3,5-trimethylcyclohexylisocyanate.

4. An isocyanate modified ester diol alkoxylate as claimed in claim 1, wherein isocyanato is 3-isocyanato-methyl-3,3,5-trimethylcyclohexylisocyanate.

5. An isocyanate modified ester diol alkoxylate as claimed in claim I, wherein from 0.04 to 0.5 isocyanato equivalent per hydroxyl equivalent is initially charged and reacted.

53.

6. An isocyanate modified ester diol alkoxylate as claimed in claim 1 , wherein from 0.04 to 0.25 isocyanato equivalent per hydroxyl equivalent is initially charged and reacted.

7. An isocyanate modified ester diol alkoxylate as claimed in claim 1 , wherein in said Component (A) m has a value of 2, n has a value of 1, x plus y have an average value of 4 and R is methyl, and said Component (B) is 3-isocyanatomethyl -3,3,5- trimethylcyclohexylisocyanate.

8. An isocyanate modified ester diol alkoxylate as claimed in claim 1, wherein in said Component (A) m has a value of 3, n has a value of 1, x plus y have an average value of 4 and R is methyl, and said Component (B) is 3-isocyanatomethyl-3,3,5-trimethylcyclohexylisocyanate.

9. An isocyanate modified ester diol alkoxylate as claimed in claim 7, wherein the average value of x plus y is 2.

10. An isocyanate modified ester diol alkoxylate as claimed in claim 7, wherein the average value of x plus y is 6.

11. An isocyanate modified ester diol alkoxylate as claimed in claim 7, wherein the average value of x plus y is 10.

12. A high solids composition comprising an isocyanate modified ester diol alkoxylate as claimed in claim 1 and additionally containing from 25 to 200 weight percent thereof of a crosslinking agent.

54.

13. A high solids composition as claimed in claim 12, wherein said crosslinking agent is hexamethoxy-methylmelamine.

14. A high solids composition as claimed in claim 12, wherein a low molecular weight polyol having from 2 to 6 hydroxyl groups and a molecular weight of from 62 to 1,000 is additionally present.

15. A high solids composition as claimed in claim 12, wherein a polycaprolactone polyol is additionally present.

16. An isocyanate modified ester diol alkoxylate as claimed in claim 1, said alkoxylate capped with from 0.1 to 1 anhydride equivalent per hydroxyl equivalent initially charged with an intramolecular anhydride of a polycarboxylic acid.

17. A high solids composition comprising an anhydride capped isocyanate modified ester diol alkoxylate as claimed in claim 16 and from 25 to 200 weight percent thereof of a crosslinking agent.

18. A high solids composition as claimed in claim 17, wherein said crosslinking agent is hexamethoxy-methylmelamine.

19. A high solids composition as claimed in claim 17, wherein a low molecular weight polyol having from 2 to 6 hydroxyl groups and a molecular weight of from 62 to 1,000 is additionally present.

55.

20. A high solids composition as claimed in claim 17, wherein a polycaprolactone polyol is additionally present.

21. A high solids composition comprising a blend of an aqueous acrylic latex and from about 5 to about 50 weight percent, based on the total solids content of said latex of an isocyanate modified ester diol alkoxylate as claimed in claim 1.

22. A high solids composition comprising a blend of aqueous acrylic latex and from about 5 to about 50 weight percent, based on the total solids content of said latex of an anhydride capped isocyanate modified ester diol alkoxylate as claimed in claim 16.

56.