CA1120950A - Derivatives of ester diol alkoxylates and compositions thereof - Google Patents

Abstract

ISOCYANATE DERIVATIVES OF ESTER DIOL
ALKOXYLATES AND COMPOSITIONS THEREOF

ABSTRACT OF THE INVENTION

Derivatives 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.

This application is a division of Serial No.
311,491, filed September 18, 1978.

S P E C I F I C A T I O N

1.

Description

~ 11855 BACK~:ROUND OF THE INVEN~ION

Government~l regulati~ns have placed ever ~ncreasing restrirti~ns on the amounts ~nd types of organl c volatlles permitted to escape into the ats-phere from coatirlg compo~itions. Consider~le efforts have b~en ~pended t~ develop coatings compositions ~aving a ~ni~l ~mount of volal:ile ~rganic components srld this h~s led to ~e development of powder coatillgs, radiatios~-curable coati~gs, and water-bor~e coatings.
10 Eligh ~olids coat~ngs represent a~other attractive technology to reduce solvent emissions. In these re-cent developme~ts, the amounts of organic ~olverlts present are f~inimal and cosls~uent1 y there is little or no at~o~pheric pollution.
A cor~spound often used in t:he pr~uction of coatislg ~d ink formul~tions is 2 ,2-dimethyl -3-hydroxypropyl 2, 2-dime~chyl-3-hydroxypropionate ~al~o known as ED-204). Howe~Jer, th~ ~ormally solid nature of ED-204 and other ester ~iol~ has on occasion 20 presented sDme problems in use. It hss been recently discovered that ester diols can be reacted with alkylene oxldes to form liquid vehlcles which, depending upon the partieular alkylene oxide selected, can be either water soluble or water insoluble; these have been called ester diol alkoxy~ate~ y further d~ scoveries ~at would also serve to ~ower atmospheric pollution would be of in~erest for use in industry.

2. ~i 09~0 11~55 - C -1 SU~IARY Oli THE I~ENTION

It has now been found that certain desiva-ti~Jes of the ester diol ~lkoxylates can ~e pr~duced that are useful in ehe production of ooati~g and ink forsnuLations. These derivat~ves are obta~ned by re-acting an ester diol alkoxylate with an intra~olecular polycas~oxylic &cid ~nhyd~ide, or an or~anac poly-isocyanate, os a polyepo:cide, or combina~ions thereof.
The resulting products ha~e beer~ fousld useful in the 1~ production of high solids oorlIpositioT~s. These high ~oli ds compositions additionally contain cross-lir~}cers ~nd can contain pigment, solvents, flow con~rol agent, plus sny of the other additives conve~:ionally pse~ent ~n a coating or ink. They cas- also be blended ~th o~her polymess and latex~s to yield co~positions that pro duoe dry f ilms having acceptable propErties .
~ESCP~IP$ION OF r~: INVEMTIpN
lrhe ester diol alkoxylate deri~Ja~ives, as ~ell as the ester diol alko~cylates themselves, ~nd ~0 the 2nethods for theis productiol~ are discussed in de-tail below.
The Ester Diol AlkoxYlates Il The es~er diol alkoxylates belong-to a new elass of materials jus~ recently discovered and ~he subiect m~tter of a different application~ These ester diol alko~at~s are produced by the rPac~ion of an ester diol of the structural formula:

11~55-C-l I. H0CnH~nccnH2nOocccn~2noH
R R

~ith an oxirane co~pound, preferably an alkylene oxide, ~o produce the ~ster diol alkoxvlate of the structural formula:
R R
II. H(~C~ 2~)xO~n~2nCC H2n00CCCnH2nO(C~H2~03 R R

wherein m is an integer having a value of from 2 to 4, prefera~ly 2 or 3; n is an ~nteger having a value of from 1 to 5, preferably 1 ~o 3 ~nd nost preferably 1; x and Y
are ineegers each having a value of from 1 to 20, prefe ably 1 to 70; R is an un~ub~titu~ed or substituted, linear or branched alkyl group having from 1 ~o 8 carbon ato~s, preferably 1 .o 3 car~on atons7 The substituents on the R gsoup ca~ be any inert group that will not interfere wn.th the reactions mvolved and can be, fos e~a~ple, cyano, halogen, alkox~l, nitro, tertiary amine, sulfo, etc. In the formulas, the variables R, m, ~, ~ and y can be ~he ~ame or different at the various locations.
The novel ester diol alkoxvlat2s (II) are pre-ferably produced by the ca~alytic reaction of an ester diol ~I) with an alkylene oxide or ~ ures of alkvlene oxides at an elevated ~e~perature as ~ore fully discus-sed belo~. One can manufacture the mono, mixed, bloc~ed or capped adduct .

;~

The alkylene oxides ~uitable for use in the production o~ the ester diol alkoxylates are the oxirane comp~unds ~uch as ~tyrene oxide, ethylene oxide, 1,2-pro-pylene oxide, 1,3-propylene oxide I 1,2-butylerle oxide, 1,3-~utylene ox~de snd 1,4-butylene oxide as well as gim~lar higher aliphatic monoepo~ides.
The ester dio ls of fo~la I in~ lude 2 ~ 2~ di-~ethyl-3-hydroxypropyl 2,2-dimethyl-3-hydroxypropionate;
2~2-dimethyl-4-hydroxybutyl 2,2-dimethyl-3-hydroxypro-pioRate; 2,2~d~methyl~4-hydroxybutyl 2,2-dimethyl-4-hy-drsxy~ut~rste; 2 9 2 - dipropyl-3-hydro~ypropyl 2,2-dipropyl-

3-~ydro~yproplonate; 2-ethyl-2 butyl-3-hydroxypropyl 2-ethyl-2-butyl-3-hytroxypropionate; 2-ethyl-2-~ethvl_3 hydroxyprvpyl 2-ethyl-2-methyl-3-hydroxypropionate;
~nd the li~
During the reaction of the ester diol I with ~he alkylene ~xid~ a catalyst ~s preferably used in ~ -caealytically effeetive amount. lhe amount of catalyst is frwm 0.01 to ~ weight percent, prefer bly from Q.05 to 0.5 weight percent, ba~ed on the comhined weights of ester d~ol I ~nd alkylene oxide. The catalysts useful are known to ~hose sk~lled in ehe art of alkylene oxide addition chemist~y and require little further discussion here. Illustrative ~hereof ~ne oan mention boron tri-fluoride etherate, potassium, potassium hydroxide, sodium, sodlum hydroxide, Lewis acids, sodium ethoxide3 mineral acids, and the like.

. ~ 5.

5~

The ~eacti~n of the ester àiol with the slkylene o~c~de ~s csrried out a~c a tempera~ure of fr~
20~ to 150C, preferably from 50 eO 120C. for ~ period of time ~ufficient to complete the react~ o~ betwees~ the reactants charged. The temperaturP is ofte~ dependent up~n the part~culax catalyst selected ~nd the alkylene o:cidP employed. The sime will vary depending upor~ the size of the bateh and the particular reactants and cat-~lys~s, snd ~he reaction conditions ~mployed.
1~ The reac~ion can be conducted at subatspheric, atmospheric or superatmospheric press~sre. The pressure is not ~ri ical alld sufficient pressurP is generall~ used to ret~in the resctants ir~ the reactor in liquit form.
The a~nt of alkylene o:~ide eharged to the re-~ction is from about 2 ~noles to about 40 moles, or more, per ~ole of ester diol charged; preferably fr~m 2 to 20 ~olesO
To minimize oxidstive side reaotions the re-act$on i5 preferably carried out under an inert gas at-~ sph~re usi~g.n~trogen, argon o~ other iltert gas.
If desixed an inert ~olvent such a~ toluene, ben-zene or l,l,l-trichloroetlane ean be employed. ~owever, the reaction proceeds well in the absence of any such sol-vent. In most instances a solvent is not required as the e~ter diol 1~ itself ~ liquid at ~he elevated temperatures em~loyed and serves to maintain a liq~tid reaction system.

At the conclusion of the reaction the prod~tct~
oon~isting of a mLxture of ~he novel est~r ~iol 6.

11855-C -l ~lkoxylates ~ ~ 5 secovered as a s~esidue product and can ~e used ~as cuch; distill~tiosl procedures can also be used to recovex more refined pr~ducts.
The ester diol alkoxylates can be used ~s s~lvesl~s, vehicles in paint or ink f~rmul~tions, w~ter-~orne coaeings, a~ an lsltes~ediate in the production of l~ther valuable compounds asld 8S a ~urfactant as well glS ~ producing t~e terivatives of this inverlt~on.
In a typical e~odiment, the ester diol and 10 catalyst ~re chasged to the seactor and the alkylene ox~de is then added over a period of time while main-t~in~ng the des ired temperature and pres sure . At the com~letion of ehe addition the c~ntents of the reactor are maintained at ~e seleceed conditions until substan-tia~ly All of the alkylene 02ide has react@d. The product can then be pur~f~ed, if tesired, ELnd recov2red by c~n-ventional procedures. I~ some ins~ances ~ne may obtain a product co~t~ini~g othes glycols as by-products. This can be minimized ~y proper ~election o reactl~n conditi~ns and cat~lyst.
The Anhydride Modiied Ester Diol Alkox~laees III
Th catalytic reaction of the e~ter diol alkoxy-lates of formula II with an intramoLecular polycarboxylic scid anhydride produces a derivative that contains free carboxyl groups. Th s can be illustra~ed by ~he following formNla, in which phthalic flnhydride is ~mployed for il-lustrative purposes, that shows the resultant product s~

118S5- C-l ÇOOH ~OOH
~CûO-IT-Ol)C _~

obtained by the reac'cio~ of two moles of phthalic a~nhydride per le of ester diol ~lkoacylate II.
Illustr~t~Ye ~f ~uitable polycarboxylic acid as~hydrides ehat c~n be u~ed ~ne can ~ention tr~melll~ic ~nhydn.de, 1:etsàhydroph~halic aI2hydridg, phthalic ~ydride, benæophenone ticar~o:~ylic acid ~ydride, succinic anhydride I ~aleic anhydride, 1~ ~aphthoic anhydrite 9 glutaric a~hydride, or any other i~tra~olecular anhydr$de, including tho e having su~-~eituents thereon such as halogen stoms, ~kyl or alko~cy groups, nitro? ca~o:~yl, ~ryl, or any other ~up which ~ill r~ot ~aduly $rlterfere ~ith the reaction.
The amo~mt of polycarboxylic acid as~hydride rea~ted ~ith the eseer diol a9kuxylate II can be ~Ln ~mount suficie~t to pennit reactioss with 811 of ~he hydroxy groups; howeY~r, it is preferred to use an aIla~t whlch is ~sufficient to react with all of the 20 hydro~cy groups present in the ester diol alkoxyl~ce II
or derivative thereof. This amount will vary and carl be frQm 0.1 to 1 anhydride equivalent for each hydroxyl equivalent or group present in the ester diol ~lko~y- -late II initially charged to the reac~ion mix~ure and is preferably from 0.1 to 0.6. In a most preferred in-~tanc~, or~e anhydride equivalent or anh~dride moiety .

5~

~` 118;5 is charged for each hydroxyl equivalent or group in-itially present ~n the reac~cion ~xture. Ia~ the r~action a eonvencional ester~ficat~ on ca~calvst can be used~ These are well known to those skilled in the ast .

The ester diol alkoxylate II ls reacted with the polycarboxylic Rcid anhydride at ~ temperature of from about 75 to 200~, prefera~ly from about 100 to 150C. The tislle required for reaction will Yary depend-ing upon the pas~acular reac ants charget, the t:emper~ture, and the baech ~lze of the reaction mixturP, facts whieh are well kno~ to those ~killed in ~he ~rt. General:ly, it has been fouIId s.hat a reaction pesiod in the la~ora-tory of frorr~ 15 eo 60 minutes at rom 125 to 150~ is ~dequate to produce the init~ial carboY~yl-modified ad dition reactisn product obtained by the reaction of these two ~ter~ediates.
The ~nhydride modified e~ cer diol alkoxylate III of ehis reaction is a visco~ss liq~lid, in ~st ~
2D ~tancesO However, ~n ~ome instances it has been obse~ed that the product w~ll solidify upon standis~g ~t soom tem-perature for ~ extended period o time. This, however, does ~ot detract from its fllrther utilityO Generally, these modified adducts are soluble in both water and ~olvents .
e Isocyanate Modified Ester_Diol Alkoxylates IV

The caealytic reaction of the ester diol alkoxylates II with a polyisocyanate produces a hydroxyl a~

11855-C-l terminaeed derivati~e that contains urethane groups IV.
This can be ~llustrated by the ollowing equation, i~
which OCNXNCO represents ~ diisocyanate, and shows the react~on of 2 mDles of II with ~ne mole of a diisocya-nate: 0 2 II ~ OCN2NC0 ~ OCNHXXNC0-II
(IV3 The polyisocyanates ~hat. c&n be used in this lnvention ~re well kn~wn tD ~hose skilled in the art and ~h~uld not require detailed description herei~. Any of the polyisocyanates can be used ~lone or in admixture with other isocysnates including the monoi~ocyanates.
Illustrative thereof one can men~ion methyl isocyanate, ~thyl isocyana~, chloroethyl isocyan~e, chloropropyl i~ocyanate, chlorohexyl i~oeyanate, chlorobutoxypropyl is~cyanate, he~ylis~cya~ate, phenyl isocyanate, the o-, ~-, and p-chlorophenyl isocyanates, benzyl isocya~2te, n~phthyl isocy~naee~ o-ethylphenyl isocyanate, the di-chlorophenyl ~socy~nates, ~utyl lsocyanste, n-propyl iso~yanaee, oetadecyl isocyanate, 3,5,5,-trimethyl-1~
i~ocyan~to-3-isocyanatsmethylcyclohexa~e"li(2-isocya-natoethyl)-bicyclo-(2~2 l)-hept-5-ene~3-dicarboxylate~
2,4-tolylene diisocyanate, 2,6-tolylene diisocyana~e,

4,4'~diphenylmethane diisocyanate, dianisidine dii~o-cyanate, tolidine diisoc~anate, hexamethylene diisocya-~ate, dicyclohexyl-4,4'-methane diisocyanate, cyclohexane-1,4-diisocyanate, 1,5-~aphthylene diisocyana~e, 4,4'-diiso-cyan~to diphenyl ether, 274,6-triisocyanatotoluenel 4,4', 10 .

! ~.

A~

11855 -C-l 4"-triisocyanato eriphenyl methane, diphenylene-4,4-diiso-cyanate, ehe polyneehylene polyphenylisocyanates as well as any of ~he other organic isOCyanates known to the average skilled chemist.
The a~unt of cster diol alkoxylate II used can be an a~ount sufficie~ to permit reaction of the isocyanato group with up to about 0.9 equivalent to the total number of hydroxyl groups present. Thus, fro~ 0.025 eO 0.9 isocyana~o equivalent is reacted per hydroxyl equivalent, preferably frQ~ 0.04 to 0.5 isocyanato equivalen~
per hydro~yl equivalent, and most preferably from 0,04 to D.25 isocyanato equivalent per hydroxyl equi~alent initially charged. The conventional urethane reaction catalvsts are used.
The reaction of ester diol alkoxyla~e II with isocyanate is conduct~d ~t a temperature of from about 25C
to 100C preferably from about 40C to 60iC. The time required will ~ary dependin~ upon the particular reactants charged, catalyst, temperature, and ehe batch size of the reaction mix~ure, facts which are well known eo ~hose ~killed in the ar~. Generally, it has been found that a reacti~n period of from 1 to 5 hours a~ from about 40 to 60C, is adequate to produce the u~ethane-modified product.
This product IV can be used per se or it can be capped or modified with a carboxylic acid anhydride by the reaction of this hydroxyl terminated ~socyanate modified ester diol alkoxylate IV with an intramolecular oarboxylic ~cid anhydride by the same procedures here-inbefore described for producing the anhydride modified .

~1 .

~ 11855 ~-1 ester diol ~lkoxylates III. In this instance the com-pounds produced can be represented by the ~,eneral sch~ tic formula:

I_ COOH O COOH
~3--COO~ OCNHX'n~CO~ OOC~

which shows the product obtained by the reaction of IV with phth~lic ~nhydride when fully capped.
The EPOXide Modified Ester Diol Alkoxylates V
The caealytic reaction of the ester diol alko~sylate II with a diepoxide ælso produces a hy-droxyl ter~inaeed desiva~ive. This can be illustra-ted by the following equation in which two moles of .
Il reaet with one mole of ~ tiepoxide to produ e V:

2 TI ~ o~0 II ~ ~V~~ ~ V) OH ~H

in which ~l 1 0~
~ represents ~ ~iepo~lde.

11855 _ C- 1 The diepoxides that can be used in this invention ~re well known to those ~killed in the art and ~re fully descr$bed in U. S . Patents 3 ,027, 35?; 2,890,194; and 2,890,197. Of particular in-terest ls ehat portion of U. S. 3 ,027 ,357 begin-ning ~t column 4, line 11 to column 7, line 38, w~ich p~rtion and disclosure is Rpeciically ln-corporated herein by reference. Among som~ o;E rhe speclfic illu~trative diepoxides disclosed herein 10 one can mention 3,4-epoxycyclohe~cylmethyl-3,4-ep-oxycyclohexarle carboxylate, ~is(3~4-epoxy-6~ ethyl cyclohexylmethyl)~dipate, bis (2,3-epoxycyclopentyl) ether, vinyl cyeL4hexene dioxide, 2-(3,4-epoxycyclo-hexyl)-5,5-~piro-(2,3-epoxycyclohexane)-~-dioxane, ~is(3J4-epo~ycyclohexylmethyl)adipate, and the like.
~he cycloalip~tic diepoxides are preferred.
The amount of diepoxide charged to he re-ction can vary fro~ about 0.2 mole per m~le of ester dio1 alkoxyla~e $I ~nitislly charged to ~he reaceion t~
as high as one le of diepo~ide per ~le of ester diol alkoxylate IX. Preferably 1~ is frosl about 0.3 to 0.6 mole of diepoxite per m~le of ester diol alk-o~ylate II initially charged. Conventional epoxide reaction catalysts ~re used.
Reaction ~ the ester diol alko~yl~te II
with an epoxide is conducted at a temperature of from about lû0C to 250C3 preferably from about 140C to 160C

13.

11855-C-l i~ ~he presence cf ~he known conventional catalysts.
Ihe tlme required will vary depending upon the par-ticular re~ctants charged, c~talyst, temperature, and batch size o~ the reactiDn m' ture, facts which are well known to those killed in th~ ~rt. Generally, it has been found that a reaction period of from 2 ~o 10 hours from about 140 to 200C, is adequate to pro-duce the epoxide-modified product. This product can be used per se or it can be capped or modified with a carboxylic ~cid anhydride ~y the reaction of this hy-droxyl terminated epo~ide modified ester dlol alkoxy-late V with an intramolecular carboxylic acid anhydride by the same procedures hereinbefore described for pro-ducing the anhydr~de modif~ed ester diol ~lkoxylates III.
In th~s instance the compounds produced can be repre-~ented by the general schem~tic formu1a:
V A

COOH COOH

COO~ 3 ~ ~ OOC
OH ~

which shows the product obtained by reaction of V with phthalic anhydride when fully capped.
Formulated ~OmPOSitiOslS_USin~ Polyols The modified ester diol alkoxylate derviatives of the types represented by fo~ulas III, I~, IV A, V
and V A can be formulated to produce coating and ink 14.

~ 11855-C-l compositions by the addition thereto of crosslinkers, polyols, pigments, filless, ~d o~cher additives con-ve~tionally used in the production of coatings and inks .
Xn prcducing the formulated cGmpositions ~ crosslinke~ such as a methylolated ~el~ne c~n be used in an ~unt rom 25 'co 200 wei~;ht percent, pre-ferably from 25 to 100 weight percent, of the sllodified e~ter diol alko~ylate charged. These compounts are 10 well krlo~ ard many ar~ commercially a~ailable. Those ~uitable for use can be represented by the general ~or~la:

~'J` ,, '2 wherein X is hydsogen or -CH20CE13 and whesein at least two of the X substituents are -CH20CH3 groups. The preferred m~lamine derivatives are the highly methyl-olated melamines, with hex~me~choxymethylmelami$le mos~preferred. Other amin4 resins ~hat can be used incLude the urea and b~nzoguanamine re~ins.
I~ addieion on~ can have present n non-volatiLe l~w molecular weight polyol containing from 2 to 6, preferably 2 to 4 hydroxyl groups. These ~on-volatile lo~ m~lecular weight polyols can have a molecular ~eight of from 62 to about 1000, 'rhey can be aliphati~ cyclo-aliphatic or srom~tic in nature. Illustrative th~reof ~e can mention ethylene glycol, diethylene glycol, tri-30 ethylene glycol, propylene gylcol, dipropylene glycol.

`L5 .

118~5 - C-l ~opentyl glycol, ~utyl~e glycol, 2 ,2-dimethyl-3-hydro~ypropyl 2 9 2-di~thyl-3-hydsoxypropionste, 2, 3~dibro~o-1,4-but-2 e~e diol, bisphenol- A and the e!ehylene o~ide and/or propylene oxide adducts there-of, 2 ,2-dihydroxy~ethylpropionic ~cid, trimethylol ~thasle" trimethylol propane, pen~aerythrito'L, di-pentaerythritol~ glycer~ne, ~orbitol, hydrogenated b~.sphenol-A; 191-dihydroxy met~ane cyclohexane, 2,2'-d~ydroxys~ethylbicyclo [2 . 2 . 1] heptane y 1, 5~ pentane 10 diol, decane diol9 and the like. Many other non-~olatile low ~olecul~r weight diols having a molecular b~ei~ht of fr~n 62 to sbout 1000 are known and can be u~Yed; the above en~Imeration is ~llustrative only.
Furthes, one can have present any of the known polycaprolacton2 polyo~ s t~a~c are eom~ercially available an:l that are fully described, f~r e~cample i~ IJ.S~ 3,169,94~. As descri~ed in this paten~c the polycaprolact~ne polyols are produce~ by the catalytic poly~erization of an exces~ of ~ caprolactone ~nd ~n 20 organlc polyf~mcti~r~al initiator having at least ~wo rPact~e hydro~en a~os3ls. The method for producing the polycaproLactone polyols ~ of no consequerlce and the organic funct~onal init~a'cor~ can l~y any polyhydroxyl compou~d a~ i~ sho~ in 1~. S . 3 ,169, 945 . Illustr~tive thereof are the diol~ such as ethylene glycol, diethylene glycol, triethylane glycol, l,~-propylen~ glycol 9 dipro-pylene glycol, 1,3-propylene glycol, polyethylene glycol, polypropylene glycol, po~y (oxyethylene-oxypropylene) glycols, ~nd similar polyalkylene glycols~ either bloc!~ed, 30 capped or heteric~ contain~ng up to about 40 or ~ore 1~ .

11855-C-l ~lkyleneoxy units in the molecule, 3 methyl-1-5-pentane-diol, cyclohexanediol, 4,4'methylene-bis-cyclohe~anol, 4,4'-isopropyliterle bis-cyclohexanol, xylenediol, 2-(4-hydroxy~e~hylphenyl) ethanol, 1,4 butanediol, snd the like;
triols ~uch as glycProl9 trimethyl~lpropane, 13296-hexane-triol, triethanolamine, triisopropanolamine, and the like;
tetrols such as erythritol, pentaerythritul9 I~,N,N' ~N'-tetrakis ~2-hydroxyethyl)ethylene diamine, ~nd ~e like.
When the organic functional initiator is re-a~cted with the caprolactone a reaction occurs that can be represented in its simplest form by the equation:
o R (X~X + ~1 ~CER' ~ R"( ~OC(CR 2)4CHR ~mOH)x O
In this e~uation the organic functionsl initiator is the R"~ com~oun~ a~d eh~ caprol~ctone is t~e O~C~CR'~)4CHR' ~

compound; this can be caprolactone itself or a substituted caprolactone wherein R' is an alkyl, alkoxy, aryl, cyclo-alkyl, ~lkaryl or aralkyl gro~p having up to twelve c~r-bon atoms and wherein at least six of the R' groups are hydrogen atoms, as shown in U.S. 3,16~,945. The poly-caprolac~one polyols tha~ are used are shown by the formu-la on the right hand side of the equation; they can have an average molecular weight of from 290 to about 6,000.

17.

11855 ~-1 ~he preferred polycsprol~ctone polyol com~ounds are those hs~ing an average molecular weight o from about 290 to ~b~ut 3,000, prefesably from about 300 ~o 1,000. The mQ~t preferred ~re the polycaprolactune dlol com~ounds ~aving ~n ~verage lecular weig~t o fro~ 290 to ~bout 500 ~nd the polycaprol~ctone triol compounds ha~i~g ~n ave~age molecular weight of from a~out 300 eo ~bout 1,000;
th¢se are most preferred because of ~heir low viscosity properties. In the fo~mul~ m is an i~teger representin~
the ~v~rage num~er of repeating units needed to produce ~he cQmpound having said lecular ~eights. The hydroxyl num~er of the polycaprolaceone polyol can be from about 15 to 600, prefer~bly from 200 t~ 500; ~nd the polycapro-lactone can have an average of fr~m 2 to 6, preferably 2 to 4, hydroxyl groups.
Illustrat~ve of useful polycaprolactones that can be u~ed ~n the formulated compositions oae ca~ me~
ti~n ~he reactlon products of a polyhydroxyl compound ha~i~g ~n ~erage ~ro~ 2 t~ 6 hydroxyl groups wi~h capro-l~ctone. The mænner in which these type polycaprolactonepolyols is produced is ~hown in U.S. 3,169,945 and m~ny such compositions are co~merci lly available. In the following t~ble there are listed illustrative polycapro-lactone polyols. The irst column lis~ the or~anic ~unctional in~tiator that is reacted WLth the caprolac-tone ~nd the average molecular weight of the polycaprD
lactone po~yol i5 shown in the second column. Knowing the molecular wei~hts o the i~itiator and of the poly-1~.

. 11855_C-l caprol~ctone polyol one can readily deeermine the ~verage number of mDlecules of capr~lactone (CPL Units) that reacted tD produce the polycaprolactone polyol;
this figure $s shown ~n the third column.
~YPE A POLYCAPROLA ~
Average Average No.
M~ ofof CPL units Initiaeor pol~olin ~olecules 1 Ethylene glycol 290 2 2 E~hylene glycol ~03 6.5 3 Ethylene glycol 2,114 1 4 Fr~pylene glycol 874 7 ~ Octylene glycol 602 4 6 Decalenè glycol 801 5.5 7 D~eth~lene glycol 527 3.7 8 Diethylene glycol 847 6.5 9 Diethylene glycol 1,246 10 ~iethyle~e glycol 1,998 16.6 11 Diethylene glycol 3,526 30 12 Triethylene glycol 754 5.3 13 Polyethylene glyco} (MW 200)* 713 4.5 14 Polyethylene glycol (M~ 600)* 1,398 7 ~olyethylene glycol (MW lSOO)* 2,868 12 16 1,2-Propylene glycol 646 5 17 1,3-Propylene g~ycol 988 8 18 DipropylÆ~e glycol 476 3 19 Polypropylene glycol (MW 425)* 835 3.6 Polypropylene glycol (~ 1000)* 1~684 6 21 Polypropyle~e glycol (MW 2000)*2,456 4 22 ~xylene glyeol 916 7 23 2~Ethyl-1,3-hexanediol 602 4 24 1,5-Pentanediol 446 3 1,4-Cyclohexan@diol 629 4.5 26 1,3-Bis(hydroxyethyl)-benzene736 5 27 Glycerol 548 4.
28 1,2,6~exanetriol 4~6 3 29 Trimethylolpropane 590 4 ~rimethylolpropane 750 5.4 31 Trimethylolpropane 1,103 8.5 4D 32 Triethanolamine 890 6.5 33 Ery~hritol 920 7 34 Pentaerythritol 1,219 9.5 * - Average molecular weight of glycol.
The structures of the compounds in the abcve tabu-lation are obvious eO one skilled in ehe art based on 19 .

the information ~,iven. me structure of compound ~aO.
7 s:

o .. O
~ 10 [ CcEt2) sC~ r~H2 CH20CH2CH2 ~ ( 2) 5 r wherein the variable r is an intep,er the ~um o~ r ~ r ha. ~n average value of 3.7 and the average molecuLar weight is 527. Thç ~tructure of co~o~md ~lo. 20 is:

~ [ (t H~ 5~~ r (C3H6~) n C3H6 1~ ~CH2) 57 r 10 whesein the s~n of r ~ r has an ~verage value of 6 and the ~verage molecular weight-is 1,684. This ex-planation makes e~plicit the structural formulas of compou~ds 1 to 34 set for~h ~above.
The concentration of the modified e~ter diol alko~ylate derivatives of the types represented by for-~ulss III, IV, IV A, V and Y A ~n the foraml~ted compo-5ition5 can be from 20 to 80 weight percent, preferably from 25 ~o S0 weight E~ercent.
The coating CODIpOSitiO~S can a1 so con~ain ar, organic 1~ solveslt snd a catalyst as optional components. Any of the conventional solvents used in t~e coatings industry can be used at ~ concentration prefer~bly below 30 wei~
percent of the total wei~ht of the coating composition.
Whlle larger amounts could conceivably be usedD the use of larger ~mounts would destroy the hi~h sol~ds nature of the coating; solv;~nts are generally added in the small amounts 2~.

."

~ 11855-C-l indic~ted to im~rove flowabiliey during application of ~he coating com~osition t~ the substrate.
In some instance an aeid catalyst migh~ be desired to imFro~e the ~ffi iency of the melamine crosslinking reaction during curing. The concentration of the cat-alyst can ~ary from zero t~ ab~ut 10 weighe percent ~ased on the total ~eight of the coating composition, The particular cata~yst used and its concentration are depend~nt to a degree upon its catalytic activity and ~le ~ speclfic c~m~onents present in ~he coatings composition.
These caealysts are known to those skilled in the ~rt ~nd include hydrochloric acid, sulfuric acid, p-~ol~ene ~ul~onic acid, dodecylbenzene sulf~nic acid, phosphoric acid and ~ts al~yl terivatives, maleic ~cid, trimel-litic acid, ph~halic acid9 succi~ic acid, ~nt the like.
The co~tings CDmpOSitiOnS can also contain pigments, fillers ~nd ~ther additives conventionally present in cQatings compositions in their conventional quantities.

The partlcular ones sel~cted are of no consequence to the ~asic inventlon. In preparing ehe coati~gs composi;ions, ~he ingredients are mixe~ by ehe conventional procedures used in the production of paints, inks or coatings compo-sitions. These procedures are so well known to those 3killed in the art that they do not re~uire further dis-cussion hera.
The coatings compositi3ns are applied eO a surface 35~
. 11855-C-l or ~u~stsate by conventional means and then thermally cured by heating at a temperature of about 125 ~o 250aC, preferably from 150 to 200C. for ~ period of ~ime suf-ficient to obtain a dry fil~:. Generally, this time will ran~e ~rom about one to 30 minutes, preferably frcm 10 to 20 m~nuteS. ~he components present in a particula- high solids co~ting composition will detenmine the tem~erature and t~me that will ~e required to obtain an adequate cure ~nd a good film coat~ng.

m e eoatings compositions of this invention are hi~h ~olids coatings co~positions 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 i~ventio~ range from aboue 70 eo 90 weight percent of ~he total weight o the coating com~osition.
Modified L2tex C~po5itions It has slso bee~ found that the dified ester ~iol ~lkoxylate derivatives of the $ypes represented by formulas III, IV, IV A, V and ~ A can be added ~o latex compositions to im~rove the properties of the latexes;
in particular acrylic latexes.
The latexes that ean be ~sed sre known to those skilled in the art and include acrylic acid and meth-acrylic acid derived latexes as well 85 those latexes derived from their esters. These latexes are commercially available and ar~ known to be copolymers of two or more 11855 -C-l mono~ners such 8S methyl methacrylate, s~yrene, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, butyl methacrylate, methacrylic acid, acrylic acid, 20hydroxyethyl ~crylate, ~inyl chloride, vinyl aceta~e, acrylamide, 2-hydroxypropyl acrylaee, iso-butsxymethyl acrylam~de, maleic acid, glycidyl acrylate, vinylideTIe chloride, vinyl eehyl ether, butadiene, acrylonitrile, diethyl maleate, v~nyl ethyl ketone, and the like. Xllustrative of copolymer latexes are vinyl chloride/vinyl ~ etate/methacrylic acid, stryene/ethyl acrylate/methacxylic acid, methyl acrylate/styrene/
vinyl acetate/~ethacrylic acid~ and any other known latex.
.The amount of said modified ester diol alkoxyla~e derlvative that can be added to ~he latex can vary from about 5 to about 50 weight percent, based on the total ~olids content of the latex, preferably rom 10 to 20 ~eight percent. I~ is added to the latex and stirred in by conventional means to obtain uniform distribution therein. The latex formulation can aLso eontain other components generally present in latex coating compositions such ~s, surfactants, antifoamsJ bactericides, mildewicides., other coalescing acids, freeze thaw additives, light stabilizers, and the like. These are well known to those skilled in the art 9 as are ~he amounts thereof required in latex coatings, and do not need extensive ~escrip~on or discussion herein to enable one skilled 23.

.

11855- C-l - ~n the ~rt to underst~nd their use.
me late~s coatislg compositions are applied to a substrat2 by the knowr eonventional methods. They are cured by heating at a temperatu~e of about 125 to 250C, preferably ~rom 150 to 200C, for ~ period of time ~ufficient to obt. in a dry ~ilm, Generally, this time will range from about one to 30 mi nutes, preerably from 10 ~o 20 minutes. The components present in a partic~dlar ~atex coating cor~position used will determine the tempera- :
10 ~:ure and t~me that will be required to obtain an ade-~uate cure ~nd a good film coating.
In che folLowing ~xamples the products were evalu-ated according to the follow~ng prooedures, Crosshatch_adhesion refexs to a test using 10 paral-lel, single-edge, razor ~lades to ~cribe t~st :films wieh 2 sets of perpendicular lines in a crosshatch pa~ctern.
Ra'cings are based on the amoun'c of fiilm removed after applying ~nd ~ubsequently pulling a coneact ~dhesiv e tape (Scotch Brand 60~) away fr~m the surface o a scribed coati~g at a 90 degrPe angle in a fast, rapid movement, It is ~mportant to carefully ~pply and press the tape to the scr$bed coating to elimi~aate ~r bubbles and provide a good bond because adhesion is reported as the percent of film remaining on the su~strate with a 100 pescent rat-ing indicating complete adhesion o~ the film in the sub-strateO

Solvenc resistance is ~ measure of the resis~ance of 24.

,~ ~ V p~

11855 -C-l the cured fil~ to a~tack by solvents, usually acetone or methvl ethyl ketone, and is reported in the nu~ber of double rubs or cvcles of solvent soaked cheese cloth -required to remo~e one-half of a fil~ from the est area.
The test is pesfor~ed bv strokin~ the film with an aceeone satusated cheese cloth until that amount o fil~
coating is removed. The nunber of cycles required to re~ove this a~ount o coating is a ~easure of the coat-ing solvene resistance. Values greater than 100 are reported as 100 which ~eans less than one-half the film was removed af~er 100 double rubs.
Reverse imoact resistAnce ~easures the ability of . . ._ . _ a given fil~ to resist rupture.rom a falling wei~ht.
A r,ardner Im~act Tester using an eig~t-poun~ dart is use~ to test the ilms cast and c~red on the steel panel.
The daIt is raised to a ~iven hei~ht in inches and drop-ped onto the reverse side of a coated ~etal panel. The inches times pbunds, designa~ed inch-pounds, absorbed by the fil~ without rupturing is recordet as the reverse im-pact resistance of ~he film.
In this application, the following defini~ions define certain compounds that are used in the exa~ples:
Silicone Surac~ant I is ~ CH3- l ¦ CH3 (CH3)3sio- _ Si~- _ ~ iO ! - Si (C~3~3 CH3 l ~c3H6(oc2~l4)7oH
13 ~3.5 Epoxide A is 3,4-epoxyoyclohexvlmethyl-3,4-epoxycyclohexane earboxylate.

~D

~1855 -C-l I~e followi~g e~periments show the production of Bster diol alkoxylates II.
Pr2paration 0f Estes Diol AlkoxYlates II
Exper~ment A
A reactor was charged with 408 grams of freshly stripped ~olid 2,2~dimethyl~3-hydroxypropyl 2,2-dim-eth~l-3-hydroxypropionate and 1.39 grams of pvtassium metal as cat~lyst and heated to liquify the ~olid. The reactor wa5 purged with nitrogen and then over a 10 hours addi~1sn period 528 grams o ethylene oxide ~Pre added while ~aintaining a temperature o from 106~ to 114C.
After ~11 sf the ethyl~ne oxide had been added, the re-action was c~ntinued at 114~C. ~or 30 minutes to com-pleti~n~ The reaction product was neutrali~ed with 1.69 grams cf acetic.a~id and vacuum ~tr~pped at 60C. and 1 m~ of Hg pre~sure. The liquid ester diol e~oxylate r~cov~red weighed 922 ~rams as the residue product con-tai~ing a minor amount of ~y-prDduct~.
The ester diol alkoxylate produced had an average of ~bout SL~ (x ~ y of Formula II) ethyleneoxy units in the molecule. The average molecular weight was 480, the Brookfield viscosity was 194 cps. at 26C. ~o. 3 spindle, 100 rpm.), ~he specific gravity was 1.079 g/cc and the Gardnes color was less ~han 2. The water dilutability was 250. Water dilulability defines the gra~ of wat~r that can be added to 10~ gra~s of the eater diol alkoxyla~e to achi~ve a haze point.
2~.

P~ .
, . .

~ 55-C-l Following th~ procedure similar to that described in xperiment A, 792 ~rams of ethylene oxide ~nd 612 grams of 2,2-dime~hyl-3-hydroxypropyl 2,2-ti~ethyl-3-hydroxy-propionate were reacted using 2.1 rams of po~ssium satalyst. 5he ethylene oxide feed time was about 11 h~urs.
The liquid ester diol ethoxylate residue pro~uct produced weighed 1,391 ~rams; it had an average of ~out ~i~ e~hyleneoxy units in the molecule. The average molecular weight was 477, the Brookfield v~scosity was 200 cps. at 24.5C (No. 3 spindle, 100 rpm), the speclfic gravity was 1.08 g/cc and the Pt/Co color was 60. Water dilutability was 296.

Following the procedure similar ~o that deseribed in Experiment A,528 grams of ethyl~e oxide ~nd 6~2 grams of ~,2-dimethyl-3 hydroxypropy~ 2~2-dimethyl-3 hydroxy-propionate were reacted using 1 gram of potassium as 2~ catalyst. Th~ ethylene oxide feet time Wa5 abou~ 9 hours.
~ he liquid esterdiol ethoxylate residue product pro--duced weighed 1,128 grams; it has an average of about four ethyleneoxy units in the molecule. The sverage ~olecular wei~ht was 392, ~he Brookield viscosity was 168 cps. at 27C (No. 3 spindle, lOa rpm~, the specific 27.

ll~j5 -C-l gravity was 1.07 g/cc and the Pt/CD color was 40. Water dilutab~lity ~as 200.

Following the procedure similar to th~qt described ~n Experiment A 220 grams of ethylene oxide ~nd 510 grams of 2,~-dimethyl-3-hydroxypropyl 2,2-t~methyl-3-hydroxypro-pionate were re~cted using 1.1 grams of potassi~m as cae-alyst. The ethylene oxide feed time was a~out S hours.
The llquid ester tiol ethoxylate residue product produced weighed 730 grams; it had an average of about ~wo ethyleneoxyunits in the molecule. The ~verage molecular wei~ht was 295~ ~he Brookield visc~sity was 285 cps at 25C. ~No. 3 ~p~ndle, 100 rpm) ant the Pt/Co color wa~
75. Water dilutability ~as 86.
~xperiment E
A stainless steel autoclave was ch2rged with 3,011 grams of sol~d 2,2-dime~hyl-3 hydroxypropyl 2,2-dimethyl-3-hydr~xyproplonate and 18 grams of boron trifluoride etherate and the contents were heatet to 60C. Th~n the autoclave was pressured to 10 psi with nitrogen and the ethylene ~xide eed was ~tarted. A eotal of 2,604 grams of ethylene oxide was added over a period of about six hours w~ile m~intainin~
~he reactor temperature of 65 to 68C. and the pressure between 10 and 30 psi. After ~11 the ethylene oxide had been added the temperature was maintained at 65C. until no ethylene oxide pressure remained in the reactor. The product was eooled to 40C; 2 weight percent o~ m~gnesiu~ silicate neutralizing agen~ was 28.

ass ~1 ~added and ehe ~xture was stirred at 40 ~ . ~or one hour. me temperature w~s raised to 90C. ~nd held while ~ ~acuum W8S applied to remove volstile products.
~is vacu~ wa~ contlnued us~til the pressure ~n the reactor reached 5 ~m. o mPrcury. The clear/c~lorless .product was pressure iltered to re~ve insolubles.
Ihere was recovered 5~494 grams of the liquid ester diol etho~ylate residue product ~aving an average o~ ~bout four ethyleneoxy units in the molecule. lhe avera~e mole-cular ~eight was 38~, the Car~n~n Fgnske viscosity was 90 cks at 100F. and ~he Pt/Co color was 30; it had an ~cid value of 0 . 06 percent as acetic acid. Gas chromato-8~raphic analysis indicated that the product was free of neopentyl glycol ~nd its ~dducts.
In ~ similar manner the ~xed ester diol ethoxyl~te/
propoxylate i5 produced using ~ mix~cure of ethylene oxide ~nd pr~pylene o:~ide as the feed m~sterial. Likewise, the ethoxyl~te/ styroxylate is produced .

~ ~oll~w~ng ~ procedure simllar to ~hat described in Experiment A, 204 grams of 2,2-dimethyl-3~hydroxypropyl 2,2~dimethyl-3-hydroxypropionate and 440 grams of ethylene oxide were reacted at 99 to 115C. using 1.5 grams of boron trifluoride ethera~e as the ca alys~ e ethylene o~ide feed time was about 4.5 hours and the mixture was 29.

11855 ~-1 heated an Rdditional O . 75 hours after completion of the a~ddlti~n. The~ 13 grams of magnesium silicate were added Qnd the mixture was stirred ~vernaght at 50 to 65C. It W8S filtered, then stripped at 100C. for one hour t~ a pressure of Smm. Hg.
The liquid ester diol ~thoxylate residue product produced weighed 602.4 grams; it had an average of about 10 e~hyleneoxy ~mits in the molec~le. The BrQokfield viscosity was 193 cps at 30C. (No. 3 spindl2, 100 rpm) 10 the specific gravity was 1.046 g/cc and the Gardner ~olor was 1.5. Water dil~tabiliey was 15.6 Following the procedure deseri~ed ~n ~per~nent F, 204 grams of 2 ,2-dimethyl-3-hydroxypropyl 2 ,2-dim-ethyl-3-hydroxypropionate was reacted with 4b,0 gr~s of ethylene oxide using l.S grams of boron triflu~:cide ether-~te 8S the catalyst. The ethylene o:cide ~ddition eime was abou~c 7 . 5 hours .
The li~uid ester diol etho~ylate residue pr~duc~c 2~ produced weighed about 629 grams after filtering and strippir~g. It hsd an average of ~out 10 ethylene~cy uni'cs in the molecule. The CannonFenske viscosity at ï00F was 103.4 cks., the specific viscosity was 1.046 g¦cc and the Gardner color was 1. Water dilueability was 1~,4 Experimene 11 Followi~g the procedure described in Experimen~ F, 30 .

11855 - C-l 125 grams of 2 ,2-dimethyl-3-hydroxypropyl 2-2dimethyl-3-hydro:scypr~pionate ~as seacted ~t 48 to 132C with a total ~f 502 ~rams ~f ethylene oxite using a total of 1.3 grams o~ potassium as the catalyst. The ethylene c~xide feet time was about 9.5 hours. At ~he co~letion of the feed llo 9 grams of m~gnesium silicate were added and the mixture w~s stirred for one hour and ~hen cooled.
The ester diol ethoxyl~te ~as filtered hot and ~tripped tmder vacuum.
The strippet ester diol ethoxylate residue product recovered weighed about 585.3 grame. It had arl verage of about 19 ethyleneoxy units in~ the molecule. The Cannon Fenske viscosity was 115.~ cks at 100F. On standing it ~oL~dified ~t 25C. and melted at a~out 27C.

In a man:rler similar to that described in Experiment A, 805 gram~ of 2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3-hy~ro2ypropionate and 8 gra~s of boron trifluoride etherate were melted at 6~C in a reaction flssk. Over a period of about 1.75 hour~ a total 811- grams of pro-pylene oxide were added at a temper~tu~e of 57 to 60C.
The reaction mixture was st~rred about another 2 hours;
32.3 ~ra~s of magnesium silicate were added and stirred a~ about 70C for about 1.5 hours. It was then stripped at 70C for 0.5 hours ~t 4-5 m~. of mercury and ~ilterPd.
The liquid ester diol propoxylate residue product was 11~55 - C-l cle~r ~and colorless ~nd weighed 1,508 grams. It had verage of ~bout 4 propyl~eo2y units ~n ;the molecule.
~ e foll~wing examples serve to r'urther define ~his ~nventi~; parts are by weight ~less otherwise indicated.
PreparatiDn~Anhytride M~tified Ester Diol Alkoxvlates III And Fo~ul~tions ~Sereo Part A - A glass-lined ~utoclave was charged with 429 .47 parts of 2 ,2-di~aethyl-3-hydroxypropyl 2 ,2-di~ethyl 10 -3-hytroxypropionate and 2.4 parts of boron trifluoride ~hera~e, T~e mixture was he~ted to 55C and 370.5 part:s of ethylene oxide were added over a period of about 13 hour~ x~ure w~s the~ held at this temperature for four more h~urs. The~, 2 percent by ~eight of mag-nesium ~ilicate ~as ~dded Bnd the contents were heaeed to 90C and st~rred for 4 hours. ~ereafter the pressu~e was reduced ~o 20 mm Hg and the,product was stripped for our hours to re~e volatiles. Atmospheric pressure was ~e-~tored with nitrogen, the contents were cooled to 50~C, 20 ~nd transferred to a storage ~utoclave~ Five p~rts of filter ~id were added, the conten~s were mi~ed for 30 ~inutes, ~nd then f$1tered and stored. A second bateh was made in eh same manner and both batches were blended by plai^-ing the materials in a large autoclave, heating the con tents to 90 ~C, and stripping the produc~ 4 hours at 5 ms;
Hg. There was obtained a large ~uantity of ~he liquid ester diol e~hoxylate hav . ng an average of about 4 ethylene-oxy units ir, the molecule.

32 .

5~
1185~ C-l art B - A 236 . 7 grams prtion of the ~bove liquit ester diol ethoxyîate (Part A) was charged to a re-~ctor together with 163.3 grams of phth~lic anhydride and 96 grams of 2-ethoxyethyl acetate as the ~olvene.
The ~ture was stirred snd heated a~c 140 ~C for 30 min~ltes. ~e anhydrite modified ester tiol ~thoxylate III had ~he ollowing average structural formule:

COOH COOH
~ ~H3 CH3 J CO(O ~2H4) ~COCH2C GH2OO~ C C~20(C2H40)yOC~

in ~hich the ~u~ of x and y have an a~rerage ~alue of about 4.
The mixtu~e elso contained ~anreacted e~t~r diol thoxvLate l~ had a Brook~ield viscosity of 386 cps at 25Ç: and ~asL. ~cid nu~iber of 124 mgm. KOH/gm.
Part C - A coating composition was p~epared by mi:cing 10 grams of the above anhydride modified ester diol etho~ylate (~art B), 10 grams of he:ca~ethoxy~ethylmela-m~e, 0.5 gram of ~,N-dimethylethanolamine7 3 grams o 2~ distill~d water, ~nd 0.05 gram of Silicone Surfactant I.
Films were prepared by cast~ng the above composition on steel pannels with a No. 40 wire-wound rod a~d ~hermally culing ~ a circulating air 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, and greater ~an 320 in h-pounds reserve impact resis~cance.

Ir~ this composition, cure ~as achieved even in ~he ab-sence of catalyst.

4~5~
11855- C-l - A eDating c~osi~io~ w~s prepared by ~ix~g 10 gr~m~ of the &nhydride mDdified es'cer di~1 alko~ylate (Part B) of Exam~le î, 10 gram~ of hexar~ethoxymethylme-1ismine as crosslinker, 0.5 gram of ~,N-dimethylethanola-mirle, 3 grams ~f ~istilled water, 0.05 grsm of S~lic~n Surf~ctant I, ~nd 0.2 gra~n of a 40 percent ~olueian of p-toluenesulfonic ~c~d dissolved ~n ~rl or~snic solvent 8S the ~talyst. Cured ~ilms were prepared as described ~n Example l, Part C. Cur~ng for 20 minutes at 220F
~ afford~d fiL~ with 100 acetone ru}: s ~ F p~nci' hardness, and h:L~h rever~e in~pact resist3nce. A film cured ~t 250-F for 20 ~ninutes ~chieved ~ 2H pencil hardness, 100 ~cet~ne rubs~ and high reverse îm~act resistance. ~he ~proved properties obtained by the use of ~ cure cat-alys~ ~re clearly evid~.
~,~ - A series of high solids ~oating com~ositions W~5 produced by mixing 10 g~ams of th~ anhydride ~difi-ed ester diol ethoxylatg (Par~ B) of E~ca~le 1, EpDxide. A, stannous octoa~e catalyst, 0.1 gram of Sillcone Surffic~:aslt I, ~nd 1 gram of xylene. Films were prepared rom the 86 weight percent solids ~olution as described in Exampl~
1 Part C. I~ring at 200F for 20 minutes produced clear dry films. The quantities of reactants used and proper-ties of the cured films are tabulated below; all the films were smoothwith high gloss.

3~.

~,' ~. .

llB5 5 -C -1 o~lation A B C D

Exa~le ~, Part B 10 . 010 . û 10 . 0 10 . O
Produc t, g Epoxide A9 15.0 10.0 7.5 6.0 Stannous Oc~coate, ~ O . 23 0 .18 0 .15 0 .14 Rev~r~e Im~act 5 259a~ 320 3û0 1~ ln-lbs.
~cetone ~bs 100 lQ0 92. 6~
Pencil Hardness H 2H 2H 2H

Fo~ulae~un B r~presents the optlmlm thenset ch~racteris -tics . The C ~nd D o~3~1ations describe the decre~se in thermoset characteriseic~ that occur when the amount of epoxide is decre~sed and the resultant high impact and hsrdness that is achieved at th2 cure conditions used.

FormulatiQrlA i~ ~ hard coa~cLng with e~ccellent ~hermoset ch~racter~ stics.

~z~ - A. pigmented high solids coating composition was prcduced by blendirlg 100 grams of the anhydride mo~i-fi~d ester diol ethoxylate of ExQmple 19 180 grams ofti anium dio~ide pigment 9 3 grams of stannous octoate cat-alyst 9 1 gram of Silicon~ Surf~ctant I, ~nd 40 gr~ms of ~ylene ~n ~ b~ll mill overnight. Subsequen~ly, 61.73 grams vf Epoxide A and 30 grams of ~ylene was mi~ed with 200 grams of the above mixture to sfford a 77 ~ei8ht percent solid-coating composition with a Bro~kfield viscosity of 1~0 35.

centipoi6e~ at 25C. Films prepared accordin~, to the proeedure described in E~ample 1 were cured at 220aF
:Eor 20 minutes. Ihe fllm produced passed 100 acetone rubs, had high gloss, had e~cellent ~dhesi~n ~nd achie-vet a pencil h~rdness of 2H.

P~r~ A - A 360 grams portlon o ~he liquid ester diol ethoxylate of Pare A of Example 1 was reacted with 40 ~ams Df phthalic as~hydride for 30 minutes at 140C
to produce ~ phthalic modified es'cer tiol ethoxylate having a ~rookfield viscosity vf 500 cps and an acid number c)f 40 ~ngm. ~COHtgm.
In ~ qimilar manner succinic anhydrite can replace phthalic anhydri~e.
P~rt B - A coating coa~position ~a~ produced by ~nixing __ 100 grams of the above pr~duct of Part A with 100 grams of hexamethoxy~ethylx~elamine, 140 grE~ns of titanium di-o:~cide 5 ~nd 25 grams of 2~eehoxyethyl ~cetate. The mix -ture was mi~ed overnight in a ball mill. Thesl a 158.5-gram portion was ~eparated and mixed with 1 gr~ of phos-phoric ~cid catalyst El~d 25 addit~ onal grams of 2-ethoxy-ethyl ~cetate. Films prepared by the procedure describet in E:xample 1 were cured for 20 minutes at 300F. The film had gvod solvent resistance ~more ~han 100 acetone ru~s~, good adhesiont and 75 irlch-pou~ds reverse impact re~istance.

36 .

11855- C-l - A 320 grams portion of the liquid ester diol ~thoxylate o~ Psrt A o Bcmaple 1 was reacted wlth 80 gsa~ns of ph~alic anhydride for 30 minutes at 140C
to produce 8 phthalic modified ester diol l~thoxylate hav~ng ~ ~rookfield viscosity of 1,690 cps ~nd an acid rl~iber of 77 mgm. ROH/E~m.
- A coating composition was producet by charging 100 grams ol ehe product of Part A, lO0 gr~ms of hexa-lDethoxymethylmelam~ne ~ 140 ~rams o titanium dioxide, ~nd 30 grams of 2-ethoxythyl acetaee to a ball mill and rolling it overnight. ThPn a ~L6B.S-gram por l~n of the mi:cture was blended with 1.5 ~rams of phosphoric acid, 0.42 gram of Tinu~rin ~70 ~9 ~a W stabilizer marketed ~y Ciba-~;eigy), O~Ll gram of Irgan4x 1010 @~ ~a br~nched phenol antioxidant marketed 'by Ciba- Geigy), 50 grams of 2-ethoxyethyl ace~:a~e, and 4.55 grams of a po3.ycapro-lact~ne triol havi~g sm aYer~ge mol~çular ~eight o 300 a~d a~ ~verage hydroxyL nu~iber of 56~ Fi~ were pre-pared acc~r~ling to the procedure described in ~xample 1 ~nd cured for 20 minutes at 250~F. The film pro~uced was solvent resistzr~t (more than lO0 acetone rubs), had a pencil hardness of 2B, and passed 50 ~nch-pounds reverse impact resist~nce.
ExamPle 7 Part A - A 280 grams portion of the 1iquid ester diol ethoxylate of Part A of Example 1 was reacted with 120 37.
.

r~
11855 ~-1 ~rams of phthalic 3nhydride for 30 ~inutes ~t 140C.
to produce a phthalic modified ester diol ethoxylate havi~g a Brookfield YiSC~sity of 18,280 cps and ~n acid num~er of ~15 m~m. K0~/gm.
A coating co$~osition was produc@d by charg-~ng 100 ~rams o the product ~f Part A, 100 grams of hex~methoxymethy~melamine, 140 gr~ms of titanium di-~de, and 40 grams of 2-ethoxyethyl aceeate to a ball ~ill a~d rolling the mixture overni8ht. Then a 173 gram portion of the mlxture was blended with 1,5 ~rams of phosphoric ~cid, 40 grams of 2-ethoxyethyl acetate, and 4.5 grams of ehe polycaprolactone triol u~ed ~n Example 6, Part B. A ~ilm was prepare~ according to theprocedure described in Exam~le 1 ~n~ cured for 20 ~nute~ at 250F. ~he film prDduced was solvent re-~istant (~ore than lO0 acetone rubs) and had a re~
verse ~mpac~ resistance of 200 iachopounds.
Pr~paration Of IsocYanate MDdifi2d_Ester Diol Alko~
29 ~
Part A - A se~ies of is~cyanate ~dified ester diol ethoxyl~tes was prepared by reacting the ester diol ethoxylate of Part A o Example 1 with 3-isocyanato m~hyl-3,5,5-trimethylcyclohexylisocyanate (IPDI) at 45C ~or about 5 hours. The resulting pr~dusts con-tained unreacted ester ~iol eth~xylate and its hydro~yl 38.

11~55 -C- 1 ~ermi~ated ~iureth8ne tQrvative. I~e quantities re ~cted and properties of the product mixtures produced are t~bulated below:
Run .~ ~! l;~ .
E~cample 1, Part A, g, 95 90 80 85 IPDI, ~ 5 10 20 15 StaIIn~s octo~te, g 0.1 0.1 0.1 Q.l Pr~duct Properties ~rookfield visc~s~ty, 5L2 1,588 33,000 6,00Q
cps at 25C
W~tcr di lutab~ lity, gms .
waeer/100 gms. product to h~Lze point~ 166 78 21 ~@ - Aqueous c~ting cos~postions were formulated and cured ollowing the procedures described in E:xa~le 1, Pare C. ~n~ daea are summarized in 'che :Eollowing table:

39 .

11855~-1 -_ ~ "~ 0~

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41 .

D~
11~55-C-l a~ple 9 ~art A - A ~60 gsa~ portio~ o the e~ter diol ethoxyla~e o~ ~art A or' E2cample 1 was re~cted ~7ith 40 grams of IPDI

for 2 hour~ Bt ~out 50C i~ con~act with 0.~ grasn of ~t~ous ccto~te ~s catalyst to pr~duce a m~x~cure con-~eal~irlg unre~c~ed ~ster tiol ~thog~lste and its hydroa~yl tesmi~atet ~lurethanee deriv~tive.
~art B - To the ~bove react~ ure there were ~dded 3~.3 grams of ph~:halic ~ dride ~d 58.8 gra~ss o~ 2-et~xy-10 eth~ cetate. ~e mi~ture ~ss heated for 30 minutes ~t 140~C. to prDduce t~e phthal~c as~ydside partl~lly c~pped reaction product ~ture.
- A ~eries of coat~g com~ositions was prepared and ~ed ~y the proce~ures described i;l E~c~le 1. Coatlr~gs 1 to 4 were cured or 20 minutes ~!lt 350 F; coati,ng 5 was cur~ a'c 250 F . me co~osition ~nd properties are ulated below:
~ati~ 1 2 3 4 5 V~
2~ E:cample 99 Part B 8 10 ~2 10 `10 ~e~ame~oxymeth~l- 12 10 8 10 10 meLa~i~e Sil~ea~e Surfac~cant I 0.1 0.1 0~1 0.1 0.1 p-Toluenesulfonic acid ~) O O 1.25 1.25 Ethoxyethyl Acetate 2.0 2.0 2.0 2.0 2,~

Coatin~ Proper~ieq Rever~e Impact, in- lbs . 300 300 300 5 15 Aceto~e ~b~ 14 100 100 100 100 Pencil P~ardne~ 4B H3 ~lB 5H 3H

3~) Ad~esian, ~ 100 100 100 100 100 42 .

f 11855 C-l ~e ~rat$~ of Epo~cide ~dified Ester Diol Alk l~te~ V kld 61 A And Formula~ons l~hereof b~
- A 348 grs~ portion of the li~uid e~ter ti~l etha~olate of ~ar~c A of E~ample 1~ 52 grsms of Ep~cide A
~nd 1. 2 gr~ ~f ~ta~ous ~ctoate (~dded ~n two po~ti~s) were re~ct~d llt 150C for 10 hou~s. T~e ep~xide ~odified est~r diol ~tho~olate pr~uced eontairled 0~68 ~ ht per-ce~t unreacted Ep~ide ~ ~n the mixture.
10 Par~ B A ~eri~ of aqueou~ coa~ing com~ost~o~ was pro-~ucet ~d cured ~o~ ng the proce~res described ~ E~-~rpl~ 1. ~e d~a are suD~rizet in ~che follawis~g ~able:

Example 10 Pa~t A 8.0 10.0 1?.0 14.0 Hexametha~methy~eL~mine 12 . O 10 . 0 8 . O 6 . O
p-ToluenesulfGnic acid1. 0 1. 0 1. O ~ . 0 D~st~lled W~ter 2.0' 2.û 2.0 2~9 Sil~cone Sur:actant 1 0.1 0.1 0.1 0.1 2~ 209 250 ~00 ~5~ 200 250 Coat~n.~Propertie~
Reverse ID~act, in-lbs. 5 l 5 ~5 25 e~S 50 25 Ac etoT~e R~ s 10 lOû 10 100 100 lQ0 100 100 Per~cil Hardness 5H 5~ 4~1 5H 2H 5H F H

The resl~lts ind~cate that hard, thermoset coatlngs were prepared.

Part A - A mixeure of 300 grams of the epoxide modified .
3~ ester dio~ ethoxalate of Part A of Example 10, 75 gra;~s 43.

r~ ~ ~ t.,,~

llR55{:-o phthalic as~hydride ~nd 94 gras~s of 2-ethoxyethyl ~cetate w~s ~aeated ~nd re~cted for 30 ~inutes at 140 ~C. to produce the ph~chalic ~nhydride c~pped der~vative of the epoxide ~odifi~d ester diol etho2ylete having ~ Brookfield vls-~sity of 500 ~ps ~t 25 Qt .
Part B - A co~t~r~g composit~on was pr~duced by }~le~ding 12.5 grams of ~he c~pped pr~duct o Part A ~bove, 10 grams of ~examethog~ethylme~amine , 0 .1 gram of Silicone Surfact-arlt I, ~nd 2 grams of 2-eth~yethyl aceta'ce. Films prepared acc~rding to the procedure described in bca~le 1 ~ere cured for 20 m~nutes at 350F. The cured fîlms obtained achieved ~ B pencil har~ess, lO0-acetone rubs, and 3~0 inch p~ ds of reverse impact resist~nce.

_~' A_=
amPle 12 A ~eries of cos~cin~ compositio~s was pr~duced using various anhydr~de modified ester diol ethoxylates pro~uced supra ~n c~njuncti~rl with ~ law molecular weight 2~ polyol. The formul~tions and their coa'cing pr~perties ~re tabula~d below; all cl~atings were curet for 20 m~n-utes at 25D ~F .

4~.
.

3~t~

11855~C-l 2 3 4 ~ 6 F~nr~Lation 9 p~rts Ex~ple 5, Part A Adduct 8.5 7,0 0 0 0 0 Example 6, P~rt A Adduct 0 0 8.5 7.0 0 E~cam~le 7, Part A Adduc~ 0 0 0 0 8.5 7.0 Tri~Dethyloîpropane (T~P) 1.5 3.0 1.5 3.0 1.5 3.0 Bexametho~ynethylmel&mirle lO 10 10 lO 10 10 Phosphoric Acid 0.2 0.2 0.2 0.2 0.2 0.2 Silic~ne Surfactarlt I 0 .1 0.1 0 .1 0.1 0. ~ 0.1 Ethoxy eehyl Acetate 2 . 0 2 . O 2 . 0 2 . 0 3 . 0 3 . O
~_ oP ertir~
Reverse I~aet, in-lbs~ lOû ~5 25 ~5 75 ~5 Acetosle R~bs 100 lûO 100 100 lO0 100 Pencil Hardness 3H 5H 3~ SH 3H 6H
Adhes~ , X lO0 lO0 100 lûO 100 lD0 All films ~ere clear, smooth, glossy, and theset ~n charae-ter. Adhesion was e~ccellent. ~The oDlati~s corltaining ~e large am~unt of ~P were very hard a~d as a result hsd minimal impact resistarlce.
2~ ~ ~
Coating co~o~itions were produced similar to those described irl Example 12 but containing higher c~
cen~ra~l~ns of ehe Adducts and decreased trimethylolpropane concentrations . The coatings were cured at 250 ~F for 20 minuee~. The results are tabulated below.

45.

.~

~ 11855 ~- 1 Coati~ 1 2 3 4 5 6D~ 7 8 Fo~mulat~on i ~arts E~L~le 5, Part A Adtuct 9,0 9.5 0 0 ~ 0 0 O

~ le 6, }?~t A A~uct 0 0 9.0 9.5 9 9 0 O

E:~ca~le ~, Part A Adduct 0 0 0 0 O O 9.5 9.9 . Trimethy}olpropane 1.0 0.5 1.0 0.5 l.û 1.0 1.0 0.5 ~lex~ethoxymethylmel~min~ 10 10 10 10 6 . 7 15 10 10 Phosphoric acid 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Sil~co~e Surf~ctant I 0 . 2 O . 2 0 . 2 0 . 2 0 . 2 0 . 2 0 . 2 0 . 2 Ethoxyethyl Acetate ~.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 C-~D~r i~-Re-terse I~?sct, in-lbs. 25 50 S0 25 25 2S 50 75 Acetone ~ubs ~100 ~
Pencil Hard~ss 2~ 2H 2H 2H 3H H 3H 2H
Adhesion , Z ~100 Thus good overall c08ting properties were ol:~tained ~ all irlst~s~ces. Adhes~on was ~xce~ t.
~3~
A pigmeDted composition was produced by mixing 2~ 90 grams of ~e product of Part A o Example 6, 100 grams of hexamethoxymethyJmelamine, 10 gr~ms of the polycapro-lac~one triol used in Part B of E~am~le 6, 140 grams of titanium ~io~cide, and 40 grams of 2-ethoxyethyl ace~cate and rolling overnight ~n a ball mill. A l9-gram portion of ehe mLxture was blended with 0.2 gram of stannous chloride and 1 gram of 2-etho~yethyL aceta~e ~o produce 11855 - C-l ~ pi~tet coating e~ss~t~o~. A f$1m was prepared ac-ccrdl~g to ~e pr~ced~lre descrLbed i~ E~ample 1 ~nd c~red os 20 ~inu~e3 at 200F. me f~lm prDduced was solve~lt resl~t~ne (m~r~ than 100 ~etone mbs), i~act resistant ~alor~ th~ 320 inch-pounds), ~d hsd a B pOE~cil hardness.

~ri~s of coating e~rposltic~s was pro~uced ~y blOEldin~ a 3tyrenelethyl ~cs~late/~thacrylic acid/
2-hydrD~yethyl acrylate late2c composlt~ av~ ng a evtal 10 ~olid~ of 43 ~eight percene with the prDduc'c of Part A .

of E~ e 6. The ~ueous l~te~ was d~fied t~ improve its filffl~fon~ng properties and to ~seabLlsh that the ~hy~r~de mvd~ f~ed ester tiol ~lko~ylates ~ct as a re~cts~ve coale~cing ~id. The ~2ulatio~s were pro~uced by mixing the components described in t~e following table at r~Qm ~emper~ture. me product of Par~ A of E~ample 6 was di-luted to S0 weighc percent sclids with ,dise~lled water and ~eutralized t~ a pH of 7.4 wit~ ~a,N-di~ethylethanola~ne.
Ru~ 1 2 3 4 5 6 7 21) ~ osit~ on solid~
Late:1c, gsns. 10 10 10 10 10 10 10 E~ample 6, Part A adduct, gms. û 0.5 1.0 1.5 0.5 1.0 0.~
~xamethoxymeth~L~ela~na 0 0 0 0 0 . 5 0 . 5 1. 0 Water 13 . 3 13 . 8 14 . 3 14 . 8 13 . 8 14 . 3 13 . 8 Films ~ere cast on Bonderite No. 37 steeL panels with a No. 60 wire-wousld rod and allowed to stand under ambi~nt c~ndi'ci4ns overnight. 'rhe films were thar~ observed for ap-2earance asld placed i~ an oven for 20 m~nut~s at 350CF. The result are reported in the ollowing table:
47 .

11~55 -C- 1 Run 1 _ 2 3 4 5 6 7 Film Pr~perties Appearance pri~r to (1) ~1) (2) (3) (4) (3) ~3) ~:usi~8 Appeir~nce after (1) (1) (2) 1~3) (4) (3) (3) cure Acetone rubs 9 cycles No cuse 60 100 100 100 lûO lûO
ReYerse iD~act, ~n-lbs. No cure ~5 15 300 ~5 5 4H
Pencal har~ess No cure F F 2B H H 300 _____ ____,,____ _______ (13 H~avy mud cracking (2) ~Dderate ~t crack~g (3) 5~oth (4) Trace Df mud craeka~g Example 16 3?art A A reaetor equipped with a stirrer, condenser, __ .
nltrogen ~nlet tube and ther~smeter was charged wi ch 100 parts of ~he ester diol propoxylate of Experi~ent I and 5~
parts o~ phthalic anhydrade. The mi~ture was ehen heated to 140C and stirred at chis te~perature for 90 ~inutes.
The anhydride ~odifled ester diol propoxylaee adduct was clear, ~riCcous and had an acid number of 138 mg~. of KOH/g~.
A S gram portion diluted with lS grams of 2-ethoxyethvl acet~te had a Brookfield ~riscosity of 460 cps at 27 C (~Jo . 4 spindle, 100 rpm).
Part B - A series of catalvzed coating co~positions was produced, appli~d to ~teel panels using a ~Jo . 40 wire wound rod and cured. The for~ulations con~ained 0.1 ~,ra~ o Silicone Surfactant I and the followi.ng components in grams:

48 .

;~i, 11855-C~l ~or~ula~ion A ~ C D
Part A Attuct 10 10 10 10 Nexamethoxymethvlmelamine 4,3 4.8 5.6 O
Epoxite A 0 0 0 10.8 p-ToluenE~lfonic Acid 0.05 0.05 0.05 0 Seannous Octo~te 0 0 0 0,2 Butyl Acetate 3.1 ~.2 3.4 h.9 2-Etho~yethyl Acetate 3.0 3.1 3~3 4.0 For~ulations A, B and C were cured at 300 F
and D at 250~. for 20 minutes. All cured coatings had reverse and front ~mpacts greater than 320 in. lb. and 100% crosshatch sdhesion values. Formulations A, B and C
passed 100 a~eto~e rubs; fon~ulation D, G5 acetone rubs.
~he pencil hardness values of formulations A, C ant D were 2X, ~hat of B was H.
Part C - A second series of formulations was prepared identical to F~rmulations A to D but without ~he addition of any p-toluenesulfonic ~cid or stannous octoate. These are ident~fied as For~ulation~ E, F, G and H respectively.
In addition Formulation I was produce~ con~ining 10 parts of the Part A Adduct, 0.1 part of Sil~ one Surfac~ant I, 7 parts of butyl aoetate, 6.3 parts ~f 2-ethoxyethyl ace~ate and 21 parts of bis(3,4-epoxycyclohe~ylmethyl) adipate.
The formulations were applied to ~teel panels as in Part B
and cured at 300F for 20 minutes. (For~ula~ions ~ and I
were also given an initial precure of 20 minutes at 250F).
All curcd coatings had reverse and ront impac~s ~reater tha~ 320 in.-1~. and 100% crosshatch adhesion valu~s.
Form~lations G, H and I passed 100 acetone rubs; for~ulatisn 49.

1185~ - C-l E, 50 acetone rubs; for~ulation F, 75 acetone rubs. The ~encil hardness v~lues of F, G and ~ were F, that of E was H and that of H was 3H.
ExEmple 17 A pigment grind was prepared using 100 parts of the anhydride fflodiied ester diol ethoxyla~e of Example 1, Past B, 180 parts of titaniun dioxide, 2 par~s of ~.annous octanoatet 1 part of Silicone 5urfa~ant I, and 4 parts of xylene by grinding in a ball ~ill.
To 161.5 parts of the pigment grind there were added 28.9 parts of bis(3,4-epoxycyclohexyl~ethyl) adipaee, 20.35 parts of 4,4'-dicyclohexyLmethane diisocya~aee and 40 part~ of xylene and the mixture thoroughly blended to yield a furmulation ha~ing a ~iscosity of 180 cps ~t room temperature. Steel panels w~re spr~y-coated and cured at 220F and 250F to yield hard, adherent, thermoset coatings with g~od impact resistance and high gloss.
Exa~ple 18 A series of coating formu}ations was produced containing the indicated components. ~hey were then applied ~o steel panels using a No. 40 wire-wound rod and cured 2t 2200~ and 250F for 20 minutes to ~ield hard, adherent, thermoset coatings with generally excellent i~pact resistance. Each formulation contained 10 parts of the anhydride modified ester diol ethoxylate of Example 1, Part B, 0.2 part oE stannous octanoate, 0.1 par~ of Silicone Surfactant I and 2 parts of 2-ethoxyethyl acetate in addition to the epoxides identified below.

50~ `

:.,`j ..j '. ``:~?

55-C~l Isocvanate __ ~ormulation A B A
(a) 3.74 0 4.07 (b) 0 5.78 4.07 (~ 7.54 0 0.~
(d) 0 11.55 0.5 (e) 11.34 0 0.5 (~ 0 17.30.5 Epoxide B ~ bi (3,4-epoxyoyclohexyl-methyl)adipate lD Isoyanate A ~ 4,4'~dic~clohexvlme~hane diisocyanate E~a~le lg A for~ulation was produced by blendin~ 10 parts of the anhydride ~odified ester diol ethoxylate of Exam~le 1, Part B, 5.78 parts of bis(3,4-epoxyeyclohexyl-methvl~
adipate, 4.07 parts of 4,4'~dicyclohexyLmetha~e diisocyc~nate and 0.2 part of stannous oct~noate. ~ne ~1 coatings wese applied to a O.S inch ~y 1 ineh poreion of ewo 1 inch wide by 1.5 inches long metal strips. The two cDaeed edges were held togeeher wlth a paper clip and cured for 20 mi~utes at 300F. In tw~ replicate tests, it was found ~hat an average tensile force applied to the ~wo ends of ~he adhered ~trips of about 600 pounds was sequired ~o break the adhesive bond that kad been ormed, E~
A series of adhesive compositions wa~ prepared, eaeh containing 10 parts of the ankydride ~odified ester diol ethoxyla~e of Example 1, Part B, and th~ following components: 51.

~,,,,,;

11855-C-l A&esive Epoxide A 0 10 Hexametho~y~ethvlmelamine 10 0 Stannous oc~oate 0 0.2 p-Toluenesulfonic Acid 0.2 0 Adhesive (1) required an average eensile ~rce of 8.8 pounds to break ehe bond; an average tensile force of 37.5 ~as required with Adhesive (2~.

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. h 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.