Note: Descriptions are shown in the official language in which they were submitted.
~ 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 .
;~
11855- C - 1
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~
11855 -C -1
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:
NX2
~'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 .
118S5 - C - 1
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.
11855-C -1
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~
~_
~6 ~ ~ O. C7 d t~ ~ g '~
_ ~ . ~C
n ~ 0 Z ~ :
o o o ~ g o~ g ~ , o
C~
__ ~ 3
__ ~
, o o ~ oO U~ ~o o, .,.
_ ~
. ~ ~ ~ X ~ ~
_ _
C~ -~ 1~ GO~ ~ - O j
_ ~
~ U~ 2 o ~" ~
~ o ~ O -~ tO~ ~ 00 _ 00 1
~1
_ ~
~ O ~ ~ `
i
_
j S
e ~ u ~ a~
a! ~ c ~ b 3 u " 6~ ~ -. I u
_ ~ X 1 a o ~ I c
~ ~ C = ~ " O ~ ~ j
40 .
',~
.3
~ ~ 8 5 5
_ _ .
V~ r~ O ~ ~ _
d ~ ~ o~ O _ ~
_ .~ C
g ;n "~ 5 ~
o O O ~ ~ T C
l~
_ , _ _ _ _
N V
_ ~ O
O O ~ ~ ~ C ~ ~
~1, .
_
~ ~ ~ u~ -- E
_
o ~ ~~ 1~
_ _. _ _ _
o~ o
o o ~ ~ ~ C -
. _
~, o ~ _ .s
o -~ ~ o oO _ ~,
E
. _ ~ V
-
_ . , 3
o ' n~
C
C j ~ v ~ ~ ~ v a d
_~ ~ CD ê~ a ~ 1 ~ 3 ~ u ~ cl
e I~ IV tl~ w C p c ~ c
_ ¦ ~ ~ E ~8 ~ p _ ,~ ¦ ~- ~ C
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:
2 3 4
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
46 O
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~.
