United States Patent (19) (11) 4,086,294

Koleske et al. 45) Apr. 25, 1978

(54) POLYCAPROLACTONE-EPOXIDE OTHER PUBLICATIONS
ADDUCTS AND COATING COMPOSITIONS
THEREOF Noshay et al., "Epoxy/Modifier Block Copolymers', J.
Poly. Sci.; Poly. Chem. 12 (3), 689-705 (1974).
(75) Inventors: Joseph Victor Koleske, Charleston; Primary Examiner-Harold D. Anderson
Oliver Wendell Smith, South Assistant Examiner-E. A. Nielsen
Charleston, both of W. Va. Attorney, Agent, or Firm-Francis M. Fazio
(73) Assignee: Union Carbide Corporation, New (57) ABSTRACT
York, N.Y. Water insoluble polycaprolactone-epoxide adducts are
produced comprising the reaction product of a polyca
(21) Appl. No.: 690,283 prolactone polyol, a diepoxide and an anhydride of a
polycarboxylic acid. The polycaprolactone polyol re
(22 Filed: May 26, 1976 acted with the diepoxide and the anhydride of the poly
carboxylic acid has at least two hydroxyl groups in the
51) Int. Cl.’...................... C08G 63/76; C08G 63/02; molecule, a hydroxyl number of from about 15 to about
C08L 67/04 600 and an average molecular weight of from about 290
52 U.S. Cl. ............................ 260/834; 260/29.2 EP; to about 6,000. The carboxylic acid anhydride has at
260/29.2 E; 260/78.3 R; 560/180 least one intramolecular carboxylic anhydride group.
58) Field of Search ...... 260/78.3 R, 830 R, 29.2 EP, These water insoluble polycaprolactone-epoxide ad
260/834, 484A, 29.2 E ducts on reaction with an inorganic or organic base
produce water soluble, carboxyl modifier polycar
prolactone-epoxide oligomer addition reaction prod
(56) References Cited ucts which are eminently suitable for the production of
U.S. PATENT DOCUMENTS aqueous coatings compositions. Exceptionally good
3,408,421 10/1968 Kurka................................... 260/830 coatings compositions are obtained when a crosslinker
3,576,903 4/1971 Groff....... ... 260/824 is present in the coating composition.
3,723,569 3/1973 Hoeschle ..... ... 260/835
3,896,303 7/1975 Gerkin et al. ................... 260/78.3 R 56 Claims, No Drawings
 1. 4,086,294 2
POLYCAPROLACTONE-EPOXIDE ADDUCTS used in this invention. The method for producing the
AND COATING COMPOSITIONS THEREOF
polycaprolactone polyols is of no consequence and the
organic functional initiators can be any polyhydroxyl
BACKGROUND OF THE INVENTION compound as is shown in U.S. Pat. No. 3,169,945. Illus
Governmental regulations have placed ever increas trative thereof are the diols such as ethylene glycol,
ing restrictions on the amounts and type of organic
diethylene glycol, triethylene glycol, 1,2-propylene
volatiles permitted to escape into the atmosphere from glycol, dipropylene glycol, 1,3-propylene glycol, poly
coatings compositions. Considerable efforts have been ethylene glycol, polypropylene glycol, poly(oxyethy
expended to develop coatings compositions having a 10
lene-oxypropylene-glycols, and similar polyalkylene
minimal amount of volatile organic components and glycols, either blocked, capped or heteric, containing
this has led to development of powder coatings, radia up to about 40 or more alkyleneoxy units in the mole
tion curable coating and water borne coatings. In these cule, 3-methyl-1-5-pentanediol, cyclohexanediol, 4,4'-
recent developments the amounts of organic solvents methylene-bis-cyclohexanol, 4,4'-isopropylidene bis
present are minimal and consequently there is little or 15 cyclohexanol, xylenediol, 2-(4-hydroxymethylphenyl)
no atmospheric pollution. ethanol, 1,4-butanediol, and the like; triols such as glyc
A particularly well known resin used in the coatings erol, trimethylolpropane, 1,2,6-hexanetriol, triethanol
industry is the class of resins derived from epsilon amine, triisopropanolamine, and the like; tetrols such as
caprolactone. These polycaprolactone polyol deriva erythritol, pentaerythritol, N,N,N',N'-tetrakis-(2-
tives produce coating materials of exceptional and de 20 hydroxyethyl)ethylene diamine, and the like.
sirable properties. However, as in all major instances in When the organic functional initiator is reacted with
the past, they have generally been applied from organic the caprolactone a reaction occurs that can be repre
solvent solutions. Any discovery which would elimi sented in its simplest form by the equation:
nate the organic solvent would be of great importance
in the coatings industry which depends upon these ma 25
terials in many manufacturing or coating operations,
Consequently, any discovery, such as the one which is R"(IOCCCR')CHROH),
hereinafter described, which would serve to lower at
mospheric pollution and still produce a good satisfac In this equation the organic functional initiator is the
tory coating composition would be of great importance. 30 R'-(OH), compound and the caprolactone is the
SUMMARY OF THE INVENTION
It has now been found that water soluble polyca
prolactone-epoxide adducts can be prepared that can be
used for the production of water borne coatings compo 35
sitions. These water soluble polycaprolactone-epoxide compound; this can be caprolactone itself or a substi
adducts are obtained by reacting a polycaprolactone tuted caprolactone wherein R' is an alkyl, alkoxy, aryl,
polyol, a diepoxide and an anhydride of a polycarbox cycloalkyl, alkaryl or aralkyl group having up to 12
ylic acid to produce a modified polycaprolactone-epox carbon atoms and wherein at least six of the R' groups
ide adduct which is generally water insoluble. This are hydrogen atoms, as shown in U.S. Pat. No.
polycaprolactone-epoxide adduct is converted to the 3,169,945. The polycaprolactone polyols that are used
water soluble form by reaction with an inorganic or are shown by the formula on the right hand side of the
organic base. The water soluble carboxyl modified equation; they can have an average molecular weight of
polycaprolactone-epoxide oligomer addition reaction from 290 to about 6,000. The preferred polycaprolac
products resulting are then formulated into coatings 45 tone polyol compounds are those having an average
compositions. The preferred coatings compositions are molecular weight of from about 290 to about 3,000,
those that additionally contain a crosslinker. The aque preferably from about 300 to 1,000. The most preferred
ous coatings compositions are applied in conventional are the polycaprolactone diol compounds having an
manner and thermally cured to dry film coatings. average molecular weight of from about 290 to about
DESCRIPTION OF THE INVENTION 50 500 and the polycaprolactone triol compounds having
an average molecular weight of from about 300 to about
The carboxyl modified polycaprolactone-epoxide 1,000; these are most preferred because of their low
adducts or derivatives that are eventually used to pro viscosity properties. In the formula m is an integer rep
duce the coatings compositions are the adducts com resenting the average number of repeating units needed
prising the reaction product of a polycaprolactone 55 to produce the compound having said molecular
polyol, a diepoxide and an anhydride of a polycarbox weights. The average hydroxyl number of the polyca
ylic acid which mixture of reaction products has subse prolactone polyol can be from about 15 to 600, prefera
quently been converted to a water soluble form by bly from 200 to 500; and the polycaprolactone polyol
reaction with a base. As starting materials for producing can have an average of from 2 to 6, preferably 2 to 4,
the adducts one can use any of the known polycaprolac hydroxyl groups.
tone polyols that are commercially available and that Illustrative of polycaprolactone polyols that can be
are fully described, for example, in U.S. Pat. No. used as starting materials in this invention one can men
3,169,945. As described in this patent the polycaprolac tion the reaction products of a polyhydroxyl compound
tone polyols are produced by the catalytic polymeriza having an average from 2 to 6 hydroxyl groups with
tion of an excess of a caprolactone and an organic poly 65 caprolactone. The manner in which these polycaprolac
functional initiator having at least two reactive hydro tone polyol compositions are produced is shown in U.S.
gen atoms. The polyols for use herein can be single Pat. No. 3,169,945 and many such compositions are
compounds or mixtures of compounds and either can be commercially available. In the following table there are
 3
4,086,294
4.
listed illustrative polycaprolactone polyols, The first trative diepoxides disclosed therein one can mention
column lists the organic functional initiator that is re 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane car
acted with the caprolactone and the average molecular boxylate, bis(3,4-epoxy-6-methylcyclohexyl-methyl
weight of the polycaprolactone polyol is shown in the Dadipate, bis(2,3-epoxycyclopentyl)ether, vinyl cyclo
second column. Knowing the molecular weights of the hexene dioxide, 2-(3,4-epoxycyclohexyl)-5,5-spiro-(2,3-
initiator and of the polycaprolactone polyol one can epoxycyclohexene)-m-dioxane, bis(3,4-epoxycyclohex
readily determine the average number of molecules of ylmethyl)adipate, and the like.
caprolactone (CPL Units) that reacted to produce the The amount of diepoxide charged to the reaction can
compound; this figure is shown in the third column, vary from about 0.2 mole per mole of polycaprolactone
POLYCAPROLACTONE POLYOLS
Average No.
Average MW of CPL Units
Initiator of polyol in molecules
1 Ethylene glycol 290 2
2 Ethylene glycol 803 6.5
3 Ethylene glycol 2,114 18
4 Propylene glycol 874 7
5 Octylene glycol 602 4.
6 Decalene glycol 801 5.5
7 Diethylene glycol 527 3.7
8 Diethylene glycol 847 6.5
9 Diethylene glycol 1,246 0
10 Diethylene glycol 2,000 16.6
11 Diethylene glycol 3,526 30
12 Triethylene glycol 754 5.3
13 Polyethylene glycol (MW 200) 713 4.5
14 Polyethylene glycol (MW 600)" 1,398 7
15 Polyethylene glycol (MW 1500)" 2,868 2
16 1,2-Propylene glycol 646 5
17 1,3-Propylene glycol 988 8
18 Dipropylene glycol 476 3
19 E. glycol (MW 425) 835 3.6
20 Polypropylene glycol (MW 1000) 1,684 6
21 Polypropylene glycol (MW2000) 2456 4.
22 Hexylene glycol 916 7
23 2-Ethyl-1,3-hexanediol 602 4.
24 1,5-Pentanediol 446 3
25 1,4-Cyclohexanediol 629 4.5
26 1,3-Bis(hydroxyethyl)-benzene 736 5
27 Glycerol 548 4.
28 1,2,6-Hexanetriol 476 3
29 Trimethylolpropane 590 4.
30 Trimethylolpropane 750 5.4
31 Trimethylolpropane 1,103 8.5
32 Triethanolamine 890 6.5
33 Erythritol 920 7
34 Pentaerythritol 1,219 9.5
* = Average molecular weight of glycol.

The structures of the compounds in the above tabular

tion are obvious to one skilled in the art based on the
information given. The structure of compound No. 7 is: polyol initially charged to the reaction, regardless of the
reaction sequence used, to as high as one mole of diep
oxide per mole of polycaprolactone polyol. Preferably
45 it is from about 0.3 to 0.6 mole of diepoxide per mole of
O O
I polycaprolactone polyol initially charged.
HO(CH)CO)CHCHOCHCH,(OC(CH).JOH Illustrative of the carboxylic acid anhydrides that can
be used one can mention trimellitic anhydride, tetrahy
wherein the variable r is an integer, the sum of r -- r drophthalic anhydride, phthalic anhydride, benzophe
has an average value of 3.7 and the average molecular. 0 none dicarboxylic acid anhydride, succinic anhydride,
weight is 527. The structure compound No. 20 is: maleic anhydride, naphthoic anhydride, glutaric anhy
dride, or any other intramolecular anhydride, including
O O those having substituents thereon such as halogen
atoms, alkyl or alkoxy groups, nitro, carboxyl, aryl, or
HO(CH)CO(CHO), CHIOC(CH)OH 55 any other group which will not unduly interfere with
the reaction.
wherein the sum of r + r has an average value of 6 and The amount of polycarboxylic acid anhydride re
the average molecular weight is 1,684. This explanation acted with the polycaprolactone polyol is an amount
makes explicit the structural formulas of compounds 1 which is insufficient to react with all of the hydroxyl
to 34 set forth above. 60 groups initially present in the polycaprolactone polyol
The diepoxides that can be used in this invention are or formed in the polycaprolactone-epoxide adduct. The
well known to those skilled in the art and are fully amount will vary and can be from 0.1 to about 0.5 anhy
described in U.S. Pat. No. 3,027,357, U.S. Pat. No. dride equivalent for each unreacted hydroxyl equiva
2,890,194 and U.S. Pat. No. 2,890,197. Of particular lent or group present in the polycaprolactone portion of
interest is that portion of U.S. Pat. No. 3,027,357 begin- 65 the reaction mixture.
ning at column 4, line 11 to column 7, line 38, which The reactions are conducted at a temperature of from
portion and disclosure is specifically incorporated about 75" to 200 C, preferably from about 100 to 160'
herein by reference. Among some of the specific illus C. The time required for reaction will vary depending
 5
4,086,294 6
upon the particular reactants charged, the temperature ammonia, butylamine, morpholine, piperazine, triethyl
and the batch size of the reaction mixture, facts which amine, N-methyl diethanolamine, N,N-diethyl ethanol
are well known to those skilled in the art. Generally it amine, N,N-dimethyl propanolamine, triethanolamine,
has been found that a reaction period in the laboratory diethylamine, triisopropanolamine, monoethanolamine,
of from 15 to 120 minutes at from about 125 to 175' C. diethanolamine, mono-isopropylamine, diisopropanol
is adequate to produce the initial water insoluble car amine, 2-amino-2-methyl-1-propanolamine, and the like.
boxyl modified polycaprolactone-epoxide oligomer While any amine can be used, the preferred are the
addition reaction product obtained by the reaction of tertiary amines.
the intermediates. The amount of amine or base added is an amount
The water insoluble polycaprolactone-epoxide ad- 10 sufficient to neutralize essentially all of the free carbox
duct formed at this stage of the reaction is a viscous ylic groups in the water insoluble adduct and to take the
liquid in most instances. However, in some instances the pH of the reaction mixture to about 6 to 10, preferably
product may solidify upon standing for an extended 7 to 9,
period of time. This, however, does not detract from its Reaction with the amine products a polycaprolac
further utility. Generally these modified polycaprolac 15 tone-epoxide product or adduct which is predominantly
tone-epoxide oligomers or adducts are water insoluble water soluble. This water soluble adduct is eminently
but solvent soluble. suitable for the production of a water borne coating
The water insoluble polycaprolactone-epoxide ad composition. While applicants have not fully estab
ducts described above are converted to water soluble lished the structures of the adducts present in their
form by reaction with a base which can be either an 20 reaction product mixture, it has been theorized that the
inorganic or an organic base. The preferred bases are reaction can proceed along the following routes; how
the organic amines. The bases that can be used are well ever, the reaction product is a complex mixture of com
known to those skilled in the art and any of the known ponents.
bases can be used. Illustrative thereof one can mention

ROUTE 1
Step 1
OH
COOCH,
(X -- 2) (E-oh -- O
OH
OH OH OH

x(E-oh
OH OH HO
O COOCH,

OH
PCL
bH
Water Insoluble Polycaprolactone-Epoxide I
Step 2

Water Insoluble Poly- +

caprolactone-Epoxide I

OH OH OH COOH

x(EL -on --
OH OH
O
HO
COOCH, O HPCL

OH

Water Insoluble Polycaprolactone-Epoxide II

Step 3
Water Insoluble Poly
caprolactone-Epoxide II + R'N - G)
eHe
OH OH OH COONR'
PCL
x(E-on
OH
-- OH
O
OH
OH

Water Soluble Polycaprolactone-Epoxide Adduct

ROUTE 2
Step 1
 7
4,086,294 8
-continued
OH O
|
Excess OH - 2
OH O ->

O
OH HOOC OH COOH

(E-oh -
OH
coo-ri -ooc
Water InsolublePolycaprolactone Adduct
Step 2

Water Insoluble Poly

caprolactone Adduct
O“O-> COOCH

OH

HOOC OH COO OOCH + (E-oh

HO OH
COO OOC

Water Insoluble Polycaprolactone-Epoxide I

Step 3
Water Insoluble Poly- + R'N -G)
caprolactone-Epoxide I
Hébe
OH
R'sNOOC
OH COO OOCH + OH
coo-ri- OOC HO OH

2
Water Soluble Polycaprolactone-Epoxide
In the above, the unit OH represents a
PCL OH
OH

polycaprolactone triol, X is an integer having a value of

from 0 to 4 and R'N represents a tertiary amine. In
some instances, depending upon the amount of anhy
dride used in the reaction, the amount of water used to 50 carboxylic acid anhydride to obtain the Water Insoluble
dissolve the final neutralized product may be restricted Polycaprolactone Adduct shown in Step 1. This deriva
before evidence of insolubilization is noted. While this tive is then reacted, as shown in Step 2, with the diepox
theoretical explanation is presented, applicants do not ide to produce the Water Insoluble Polycaprolactone
intend to be bound by any theory. Epoxide Adduct I. Finally, this latter compound is
In a typical embodiment according to Route 1, one 55 reacted with an amine in Step 3 to produce the Water
can react the polycaprolactone polyol with the diepox Soluble Polycaprolactone-Epoxide.
ide at the indicated temperature to produce the Water In the schematics shown above specific ratios and
Insoluble Polycaprolactone-Epoxide I or variants compounds were employed for illustrative purposes
thereof. In some instances one may wish to react up to only. It is apparent, in view of our complete description,
two of the hydroxyl on each polycaprolactone triol. that these can be modified within the ranges disclosed in
This intermediate compound is then reacted in Step 2 this application.
with a carboxylic acid anhydride to form the second
Water Insoluble Polycaprolactone-Epoxide II shown theAsdiepoxide is known, catalysts are used during the reaction of
with the carboxyl group. The suitable
above. Finally, this latter compound is reacted with an 65 catalysts for use in this invention are those convention
amine in Step 3 to yield the Water Soluble Polyca ally used and the amounts are also known to those
prolactone-Epoxide Adduct shown, skilled in the art. Illustrative thereof one can mention
In a typical embodiment according to Route 2, one stannous octoate, benzildimethylamine, tris(dime
can initially react the polycaprolactone polyol with a thylaminomethyl)phenol, triethylenediamine, tributyl
 9
4,086,294
10
phosphine, triethylamine, uranyl nitrate hexahydrate, required to remove one half of a film from the test area.
and the like. . . . ...
The water soluble polycaprolactone-epoxide deriva The test is performed by stroking the film with an ace
tives or adducts prepared above can be used to produce tone soaked cheesecloth until that amount of film coat
coating compositions. They can also be modified in ing is removed. The number of cycles required to re
known manner by the addition of pigments, fillers and move this amount of coating is a measure of the coating
solvent resistance.
other additives conventionally added to coating compo
sitions. In any instance they are applied to a surface by Reverse impact measures the ability of a given film to
conventional means and then thermally cured either resist rupture from a falling weight. A Gardner Impact
alone or in the presence of a crosslinker. It is preferred, 10 Tester using an 8 pound dart is used to test the films cast
however to have a crosslinker present and in the such and cured on the steel panel. The dart is raised to a
instances the known catalyst for expediting the cross given height in inches and dropped on to the reverse
linking reaction are generally added. The particular side of a coated metal panel. The inches times pounds,
pigment or colorants added to the coating compositions dsignated inch-pound, absorbed by the film without
are immaterial and any of the known conventional ones 15 rupturing is recorded as the films reverse-impact resis
can be used. The amount of crosslinker present in the tance,
coating composition can vary from 25 to 200 weight
percent preferably 50 to 100 weight percent, based on theInparticularthis application the following definitions describe
compounds that are used in the examples:
the weight of the water soluble polycaprolactone-epox Silicone Surfactant I is
ide adduct. Among the suitable crosslinkers are the urea 20
formaldehyde aminoplasts, the hexamethoxymethyl
melamines, and the known water dispersible transethers
thereof with lower alkanols, benzoguanamine, acrylam
ide resins, as well as any of the other well known cross (CH)SiO o
H. H.o Si(CH)
linkers of the amine type. 25
CH, CH,H.(OCH),OH 5.5
Catalysts are generally present to catalyze a mela
mine or amine cure system and these are also well
known. Among the common catalysts are the mineral Polyol B is a polycaprolactone triol having an aver
acids such as hydrochloric acid or sulphuric acid, para age molecular weight of 540 and an average hydroxyl
toluene sulphonic acid, dodecylbenzene sulphonic acid, 30 number of 310.
phosphoric acid, maleic acid, trimelletic acid, phthalic Polyol C is a polycaprolactone triol having an aver
acid, succinic acid, and the like. Also useful are the half age molecular weight of 300 and an average hydroxyl
esters of said acids. It is known that the stronger the number of 560.
acidity, the better the catalytic activity. The following examples further serve to define this
The coating compositions are applied to a substrate 35 invention.
by the known conventional methods. They are cured by
heating at a temperature of about 125' To 250 C., pref EXAMPLE 1.
erably from 150 to 200 C. for a period of time suffi A mixture of 5,510 grams of Polyol C, 9,974 grams of
cient to obtain a dry film. Generally, this time will range Polyol B and 2,516 grams of 3,4-epoxycyclohexylmeth
from about one to 30 minutes, preferably from 10 to 20 40
minutes. The components presentin a particular coating yl-3,4-epoxycyclohexane carboxylate were charged to a
composition used will determine the temperature and reaction kettle. This mixture was heated to 100 C. and
time that will be required to obtain an adequate cure 150 ppm stannous octoate catalyst was added. The tem
and a good film coating. perature was raised to 150° C. and the mixture stirred at
The coatings compositions of this invention are gen 45 that temperature for 18 hours to completion of the reac
erally high solids coatings compositions and they can tion. Analysis of the polyol product produced indicated
contain as much as about 80 weight percent solids a hydroxyl number of 343, a water content of 0.03
therein. Generally the total solids content of the coat weight percent and 0.13 residual unreacted epoxy.
ings compositions of this invention range from about 30 A 280 gram portion of the above adduct was reacted
to 70 weight percent of the total weight of the composi 50 with 70 grams of phthalic anhydride under an inert gas
tion.
The coatings compositions were evaluated according atmosphere
tone-epoxide
for 30 minutes at 130 C. This polycaprolac
adduct was also water insoluble, had an
to the following procedures. Crosshatch adhesion refers RVT Brookfield viscosity of 314,000 cps. at 25° C.
to a test using 10 parallel single edge razor blades to using a No. 6 spindle at 1 rpm and an acid number of 76.
scribe test films with 2 sets of perpendicular lines on a 55
cross-hatch pattern. Ratings are based on the amount of EXAMPLE 2
film removed after applying and subsequently pulling a A coating composition was produced containing 20
contact adhesive tape (Scotch Brand 606) away from grams of the water insoluble polycaprolactone-epoxide
the surface of the scribed coating at a 90' angle in a fast
rapid movement. It is important to carefully apply and 60 adduct of Example 1, 10 grams of hexamethoxymethyl
press the tape to the scribed coating to eliminate air melamine containing about 1.5 weight percent methylol
bubbles and provide a good bond because adhesion is group, 2.7 grams of dimethyl ethanolamine, 0.02 gram
reported in percent of film remaining on the substrate of Silicone Surfactant I, and 25 grams of water. A clear
with a 100 percent rating indicating complete adhesion water soluble coating was produced which was cast on
of the film to the substrate. 65 steel panels and cured at 350 F. for 10 minutes. The
Solvent resistance is a measure of the resistance of the resulting film had a reverse impact of 50 in/lb., excel
cured film to attack by acetone and is reported in the lent crosshatch adhesion, pencil hardness of 3H and
number of rubs or cycles of acetone soaked cheesecloth excellent resistance to acetone solvent.
 11
4,086,294
12
EXAMPLE 3 A coating composition was prepared containing 165
grams of the water soluble polycaprolactone-epoxide
A 297.5 grams portion of the water insoluble reaction adduct reaction mixture of this example, 150 grams of
product produced in the first paragraph of Example 1 titanium dioxide, 45 grams of water, 135 grams of hex
was reacted with 52.5 grams of phthalic anhydride 5 amethoxy-methylmelamine having about 5 weight per
under nitrogen at 130° C. for 30 minutes. The amber cent methylol groups, 1.3 grams Silicone Surfactant I, 1
colored liquid polycaprolactone-epoxide adduct ob gram of the adduct of 10.5 moles of ethylene oxide and
tained had an RVT Brookfield viscosity of 1,030 poises nonyl phenol.
at 25° C. using a No. 6 spindle at 5 rpm and an acid EXAMPLE 8
number of 57. This product was also water insoluble. 10
EXAMPLE 4 A mixture of 140 grams of Polyol B, 140 grams of
Polyol C and 60 grams of succinic anhydride was re
A 315 grams portion of the water insoluble reaction acted under nitrogen at 140° C. for 5 minutes. To this
product produced in the first paragraph of Example 1 reaction product mixture there were added 13.4 grams
was reacted with 35 grams phthalic anhydride under an 15 of polycaprolactone diol having an average molecular
inert atmosphere at 130 C, for 30 minutes. The polyca weight of 1,250 and an average hydroxyl value of 90,
prolactone-epoxide adduct produced was a water insol 66.6 grams of 3,4-epoxycyclohexylmethyl-3,4-epoxycy
uble viscous liquid having an acid number of 40 and a clohexane carboxylate, and 1 gram of stannous octoate.
Brookfield viscosity of 470 poises at 25 C. The polycaprolactone-epoxide adduct reaction mixture
A coating formulation was produced containing 20 20 had an acid number of 40.5 and an oxirane content of 0.1
grams of the above water insoluble product, 10 grams of weight percent.
hexamethoxymethylmelamine having about 1.5 weight A 10 grams portion of the adduct described above
percent methylol groups, 1.5 grams of dimethyl etha was formulated with 10 grams of hexamethoxymethyl
nolamine, 0.02 gram of Silicone Surfactant I and 25 melamine having about 5 weight percent methylol
grams of water. This water soluble coating was applied 25 group, 6.7 grams of water, 0.8 grams of dimethyl etha
to steel panels and cured at 350 F. for 10 minutes to nolamine and 0.1 gram of Silicone Surfactant I to pro
produce coatings with good flexibility, hardness, sol duce a water soluble clear coating composition. Films
vent resistance and adhesion. cast on steel panels and cured at 350 F. for 20 minutes
gave coatings having good impact, hardness and adhe
EXAMPLE 5 30 sion properties.
A 380 grams portion of the reaction product of the What we claim is:
first paragraph of Example 1 was reacted in an inert duct 1. A water insoluble polycaprolactone-epoxide ad
atmosphere with 20 grams of maleic anhydride at 130 polycaprolactone comprising the reaction product mixture of a
C. for 5 minutes. The water insoluble polycaprolactone 35 of a polycarboxylicpolyol, a diepoxide and an anhydride
epoxide adduct produced had an acid number of 28 and prolactone-epoxide adductsaidreaction
acid, water insoluble polyca
product mixture
Brookfield viscosity of 277 poises at 25' C.
A clear water soluble coating was obtained using 10 ing of Route 1 or Route 2, wherein Routegroup
produced by a process selected from the consist
1 comprises
grams of the water insoluble product produced above in the
admixture with 6.7 grams of water, 0.8 grams of di 40 (i)steps of
reacting a polycaprolactone polyol having at least
methyl ethanolamine, 10 grams of hexamethoxymethyl two hydroxyl groups in the molecule, a hydroxyl
melamine having about 1.5 weight percent methylol number of from about 15 to about 600 and an aver
groups and 0.04 gram of Silicone Surfactant I. This age molecular weight of from 290 to about 6000
coating composition, when applied and cured at ele with a diepoxide to produce a water insoluble
vated temperature, produced good films. 45 polycaprolactone-epoxide intermediate, and then
EXAMPLE 6 (ii) reacting the intermediate of (i) with an intramo
A mixture of 297.5 gram of Polyol B and 52.5 grams lecular anhydride of a polycarboxylic acid to pro
of phthalic anhydride was reacted under nitrogen at duce said water insoluble polycaprolactone-epox
ide adduct
130° C. for 30 minutes. At this time, 52.5 grams of 3,4- 50 and wherein Route reaction product mixture,
epoxycyclohexylmethyl-3,4-epoxycyclohexane carbox 2 comprises the steps of
(i) reacting a polycaprolactone polyol having at least
ylate and 0.4 gram of stannous octoate were added and two hydroxyl groups in the molecule, a hydroxyl
the mixture was heated for an additional 45 minutes at number of from about 15 to about 600 and an aver
130 C. The polycaprolactone-epoxide adduct pro age molecular weight of from 290 to about 6000
duced was water insoluble and had an acid number of 55 with an intra-molecular anhydride of a polycarbox
37. Water soluble coating compositions were produced ylic acid to produce a water insoluble polyca
by the addition of 6.7 grams of water and 0.6 gram of prolactone adduct intermediate, and then
dimethyl ethanolamine to 10 grams of the above water (ii) reacting the intermediate of (i) with a diepoxide to
insoluble adduct. produce said water insoluble polycaprolactone
EXAMPLE 7 60 epoxide adduct reaction product mixture and
A 360 grams portion of the polyol produced in the wherein there is used from 0.1 to about 0.5 anhy
first paragraph of Example 1 was reacted under nitro dride equivalent for each unreacted hydroxyl
gen with 40 grams of phthalic anhydride at 130 C. for
equivalent or group initially present in the polyca
prolactone polyol or formed in the polycaprolac
30 minutes. A water insoluble polycaprolactone-epox 65 tone-epoxide adduct.
ide adduct was obtained having an acid number of 39. 2. A water insoluble polycaprolactone-epoxide ad
This was neutralized with 25 grams of morpholine to duct as claimed in claim 1, wherein said polycaprolac
give a water soluble adduct. tone polyol has from 2 to 6 hydroxyl groups.
 13 4,086,294
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3. A water insoluble polycaprolactone-epoxide ad polycaprolactone polyol, a diepoxide and an anhydride
duct as claimed in claim 1, wherein said polycaprolac of a polycarboxylic acid, said water soluble polyca
tone polyol has from 2 to 4 hydroxyl groups. prolactone-epoxide adduct reaction product mixture
4. A water insoluble polycaprolactone-epoxide ad produced by a process selected from the group consist
duct as claimed in claim 1, wherein said polycaprolac ing of Route 1 or Route 2, wherein Route 1 comprises
tone polyol has an average molecular weight of from the steps of
290 to about 3,000. (i) reacting a polycaprolactone polyol having at least
5. A water insoluble polycaprolactone-epoxide ad two hydroxyl groups in the molecule, a hydroxyl
duct as claimed in claim 1, wherein said polycaprolac number of from about 15 to about 600 and an aver
tone polyol is a diol having an average molecular O age molecular weight of from 290 to about 6000
weight of from 290 to about 500. with a diepoxide to produce a water insoluble
6. A water insoluble polycaprolactone-epoxide ad polycaprolactone-epoxide intermediate, then
duct as claimed in claim 1, wherein said polycaprolac (ii) reacting the intermediate of (i) with an intramo
tone polyol is a triol having an average molecular lecular anhydride of polycarboxylic acid to pro
weight of from about 300 to about 1,000. 15 duce a second water insoluble polycaprolactone
7. A water insoluble polycaprolactone-epoxide ad epoxide adduct intermediate and then
duct as claimed in claim 1, wherein said polycaprolac (iii) reacting the second intermediate of (ii) with an
tone polyol is a mixture of polycaprolactone polyols. inorganic or organic base in an amount sufficient to
8. A water insoluble polycaprolactone-epoxide ad neutralize the free carboxyl groups of the interme
duct as claimed in claim 1, wherein said anhydride is 20 diate of (ii) to produce said water soluble polyca
phthalic anhydride. prolactone-epoxide adduct reaction product mix
9. A water insoluble polycaprolactone-epoxide ad ture,
duct as claimed in claim 1, wherein said anhydride is and wherein Route 2 comprises the steps of
maleic anhydride. (i) reacting a polycaprolactone polyol having at least
10. A water insoluble polycaprolactone-epoxide ad 25 two hydroxyl groups in the molecule, a hydroxyl
duct as claimed in claim 1, wherein said diepoxide is number of from about 15 to about 600 and an aver
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane car age molecular weight of from 290 to about 6000
boxylate. with an intra-molecular anhydride of a polycarbox
11. A water insoluble polycaprolactone-epoxide ad ylic acid to produce a water insoluble polyca
duct as claimed in claim 1, wherein from 0.2 to 1 mole 30 prolactone adduct intermediate, then
of diepoxide is charged per mole of polycaprolactone (ii) reacting the intermediate of (i) with a diepoxide to
polyol initially charged and reacted. produce a second water insoluble polycaprolac
12. A water insoluble polycaprolactone-epoxide ad tone-epoxide adduct intermediate, and then
duct as claimed in claim 1, wherein from 0.3 to 0.6 mole
of diepoxide is charged per mole of polycaprolactone 35 (iii)inorganic
reacting the second intermediate of (ii) with an
or organic base in an amount sufficient to
polyol initially charged and reacted. neutralize the free carboxyl groups of the interme
13. A water insoluble polycaprolactone-epoxide ad diate of (ii) to produce said water soluble polyca
duct as claimed in claim 1, wherein said polycaprolac prolactone-epoxide adduct reaction product mix
tone polyol is a polycaprolactone triol having an aver ture and wherein there is used from 0.1 to about 0.5
age molecular weight of 300 and an average hydroxyl anhydride equivalent for each unreacted hydroxyl
number of 560, said diepoxide is 3,4-epoxycyclohexyl equivalent or group initially present in the polyca
methyl-3,4-epoxycyclohexane carboxylate and said an prolactone polyol or formed in the polycaprolac
hydride is phthalic anhydride. tone-epoxide adduct.
14. A water insoluble polycaprolactone-epoxide ad 18. A water soluble polycaprolactone-epoxide adduct
duct as claimed in claim 1, wherein said polycaprolac 45 as claimed in claim 17, wherein said polycaprolactone
tone polyol is a polycaprolactone triol having an aver polyol has from 2 to 6 hydroxyl groups, and said base is
age molecular weight of 300 and an average hydroxyl an organic base.
number of 560, said diepoxide is 3,4-epoxycyclohexyl 19. A water soluble polycaprolactone-epoxide adduct
methyl-3,4-epoxycyclohexane carboxylate and said an as claimed in claim 17, wherein said polycaprolactone
hydride is maleic anhydride. 50 polyol has from 6 to 4 hydroxyl groups, and said base is
15. A water insoluble polycaprolactone-epoxide ad an organic base.
duct as claimed in claim 1, wherein said polycaprolac 20. A water soluble polycaprolactone-epoxide adduct
tone polyol is a polycaprolactone triol having an aver as claimed in claim 17, wherein said polycaprolactone
age molecular weight of 540 and an average hydroxyl polyol has an average molecular weight of from 290 to
number of 310, said diepoxide is 3,4-epoxycyclohexyl 55 about 3,000, and said base is an organic base.
methyl-3,4-epoxycyclohexane carboxylate and said an 21. A water soluble polycaprolactone-epoxide adduct
hydride is phthalic anhydride. as claimed in claim 17, wherein said polycaprolactone
16. A water insoluble polycaprolactone-epoxide ad polyol is a diol having an average molecular weight of
duct as claimed in claim 1, wherein said polycaprolac from 290 to about 500, and said base is an organic base.
tone polyol is a mixture of a polycaprolactone triol 22. A water soluble polycaprolactone-epoxide adduct
having an average molecular weight of 540 and an aver as claimed in claim 17, wherein said polycaprolactone
age hydroxyl number of 310 and a polycaprolactone polyol is a triol having an average molecular weight of
triol having an average molecular weight of 300 and an from about 300 to about 1,000, and said base is an or
average hydroxyl number of 560, said diepoxide is 3,4- ganic base.
epoxycyclohexylmethyl-3,4-epoxycyclohexane carbox 65 23. A water soluble polycaprolactone-epoxide adduct
ylate and said anhydride is succinic anhydride. as claimed in claim 17, wherein said polycaprolactone
17. A water soluble polycaprolactone-epoxide adduct polyol is a mixture of polycaprolactone polyols, and
comprising the adduct reaction product mixture of a said base is an organic base,
 15
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24. A water soluble polycaprolactone-epoxide as 35. A coating composition comprising a water soluble
claimed in claim 17, wherein said anhydride is phthalic polycaprolactone-epoxide adduct as claimed in claim 17
anhydride, and said base is an organic base. and additionally containing from 25 to 200 weight per
25. A water soluble polycaprolactone-epoxide as cent of an amine crosslinking agent based on the weight
claimed in claim 17, wherein said anhydride is maleic of said water soluble adduct.
anhydride, and said base is an organic base. 36. A coating composition comprising a water soluble
26. A water soluble polycaprolactone-epoxide as polycaprolactone-epoxide adduct as claimed in claim 18
claimed in claim 17, wherein said diepoxide is 3,4-epox and additionally containing from 25 to 200 weight per
ycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, cent of an amine crosslinking agent based on the weight
and said base is an organic base. O of said water soluble adduct.
27. A water soluble polycaprolactone-epoxide as 37. A coating composition comprising a water soluble
claimed in claim 17, wherein in said adduct reaction polycaprolactone-epoxide adduct as claimed in claim 19
product from 0.2 to 1 mole of diepoxide is reacted per and additionally containing from 25 to 200 weight per
mole of polycaprolactone polyol initially charged, and cent of an amine crosslinking agent based on the weight
said base is an organic base. 15 of said water soluble adduct.
28. A water soluble polycaprolactone-epoxide as 38. A coating composition comprising a water soluble
claimed in claim 17, wherein in said adduct reaction polycaprolactone-epoxide adduct as claimed in claim 20
product from 0.3 to 0.6 mole of diepoxide is reacted per and additionally containing from 25 to 200 weight per
mole of polycaprolactone polyol initially charged, and 20 cent of an amine crosslinking agent based on the weight
said base is an organic base. of said water soluble adduct.
29. A water soluble polycaprolactone-epoxide as 39. A coating composition comprising a water soluble
claimed in claim 17, wherein in said adduct reaction polycaprolactone-epoxide adduct as claimed in claim 21
product from 0.2 to 1 mole of diepoxide is reacted per and additionally containing from 25 to 200 weight per
mole of polycaprolactone initially charged and from 0.1 cent of an amine crosslinking agent based on the weight
to 0.5 carboxylic anhydride equivalent per unreacted 25 of said water soluble adduct.
hydroxyl equivalent in said polycaprolactone polyol are 40. A coating composition comprising a water soluble
reacted and said base is an organic base. polycaprolactone-epoxide adduct as claimed in claim 22
30. A water soluble polycaprolactone-epoxide as cent and additionally containing from 25 to 200 weight per
claimed in claim 17, wherein in said adduct reaction 30 of said of an amine crosslinking agent based on the weight
water soluble adduct.
product from 0.3 to 0.6 mole of diepoxide is reacted per 41. A coating composition comprising a water soluble
mole of polycaprolactone initially charged and from 0.1 polycaprolactone-epoxide adduct as claimed in claim 23
to 0.5 carboxylic anhydride equivalent per unreacted and
hydroxyl equivalent in said polycaprolactone polyol are cent of an amine crosslinkingfrom
additionally containing 25 to 200 weight per
agent based on the weight
reacted and said base is an organic base. 35 of said water soluble adduct.
31. A water soluble polycaprolactone-epoxide as 42. A coating composition comprising a water soluble
claimed in claim 17, wherein in said adduct reaction polycaprolactone-epoxide
product said polycaprolactone polyol is a polycaprolac and additionally containingadduct from
as claimed in claim 24
25 to 200 weight per
tone triol having an average molecular weight of 300 cent of an amine crosslinking agent based on the weight
and an average hydroxyl number of 560, said diepoxide of said water soluble adduct.
is 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane 43. A coating composition comprising a water soluble
carboxylate and said anhydride is phthalic anhydride, polycaprolactone-epoxide adduct as claimed in claim 25
and said base is N,N-dimethyl ethanolamine.
32. A water soluble polycaprolactone-epoxide as cent of an amine crosslinkingfrom
and additionally containing 25 to 200 weight per
agent based on the weight
claimed in claim 17, wherein in said adduct reaction 45 of said water soluble adduct.
product said polycaprolactone polyol is a polycaprolac 44. A coating composition comprising a water soluble
tone triol having an average molecular weight of 300. polycaprolactone-epoxide
and an average hydroxyl number of 560, and diepoxide and additionally containingadduct as claimed in claim 26
is 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane cent of an amine crosslinkingfrom 25 to 200 weight per
carboxylate and said anhydride is maleic anhydride, and 50 of said water soluble adduct. agent based on the weight
said base is N,N-dimethyl ethanolamine. 45. A coating composition comprising a water soluble
33. A water soluble polycaprolactone-epoxide as polycaprolactone-epoxide adduct as claimed in claim 27
claimed in claim 17, wherein in said adduct reaction and additionally containing from 25 to 200 weight per
product said polycaprolactone polyol is a polycaprolac cent of an amine crosslinking agent based on the weight
tone triol having an average molecular weight of 540 55 of said water soluble adduct.
and an average hydroxyl number of 310, and said base is 46. A coating composition comprising a water soluble
N,N-dimethyl ethanolamine.
34. A water soluble polycaprolactone-epoxide as and additionally containingadduct
polycaprolactone-epoxide as claimed in claim 28
from 25 to 200 weight per
claimed in claim 17, wherein in said adduct reaction
product said polycaprolactone polyol is a mixture of a cent of an amine crosslinking agent based on the weight
of said water soluble adduct.
polycaprolactone triol having an average molecular 47. A coating composition comprising a water soluble
weight of 540 and an average hydroxyl number of 310 polycaprolactone-epoxide adduct as claimed in claim 29
and a polycaprolactone triol having an average molecu and additionally containing from 25 to 200 weight per
lar weight of 300 and an average hydroxyl number of cent of an amine crosslinking agent based on the weight
560, said diepoxide is 3,4-epoxycyclohexylmethyl-3,4- 65 of said water soluble adduct.
epoxycyclohexane carboxylate and said anhydride is 48. A coating composition comprising a water soluble
succinic anhydride, and said base is N,N-dimethyl etha polycaprolactone-epoxide adduct as claimed in claim 30
nolamine. and additionally containing from 25 to 200 weight per
 17
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18
cent of an amine crosslinking agent based on the weight ylic acid to produce a water insoluble polyca
of said water soluble adduct. prolactone adduct intermediate, and
49. A coating composition comprising a water soluble (ii) reacting the intermediate of (i) with a diepoxide to
polycaprolactone-epoxide adduct as claimed in claim 31 produce said water insoluble polycaprolactone
and additionally containing from 25 to 200 weight per 5 epoxide adduct reaction product mixture.
cent of an amine crosslinking agent based on the weight 54. A process as claimed in claim 53, wherein said
of said water soluble adduct. water insoluble polycaprolactone-epoxide adduct reac
50. A coating composition comprising a water soluble tion product mixture is reacted with an inorganic or
polycaprolactone-epoxide adduct as claimed in claim 32 organic base in an amount sufficient to neutralize the
and additionally containing from 25 to 200 weight per
10 free carboxyl groups of said adduct reaction product
mixture to produce a water soluble polycaprolactone
cent of an amine crosslinking agent based on the weight epoxide adduct reaction product mixture.
of said water soluble adduct. 55. A process for producing a water insoluble polyca
51. A coating composition comprising a water soluble prolactone-epoxide adduct reaction product mixture
polycaprolactone-epoxide adduct as claimed in claim 33 15 comprising the steps of
and additionally containing from 25 to 200 weight per () reacting a polycaprolactone polyol having at least
cent of an amine crosslinking agent based on the weight two hydroxyl groups in the molecule, a hydroxyl
of said water soluble adduct. number of from about 15 to about 600 and an aver
52. A coating composition comprising a water soluble age molecular weight of from 290 to about 600
20 with a diepoxide to produce a water insoluble
polycaprolactone-epoxide adduct as claimed in claim 34 polycaprolactone-epoxide intermediate, and
and additionally containing from 25 to 200 weight per (ii) reacting the intermediate of (i) with an intramo
cent of an amine crosslinking agent based on the weight lecular anhydride of of polycarboxylic acid to pro
of said water soluble adduct. duce a water insoluble polycaprolactone-epoxide
53. A process for producing a water insoluble polyca 25 adduct reaction product mixture.
prolactone-epoxide adduct reaction product mixture 56. A process as claimed in claim 55, wherein said
comprising the steps of water insoluble polycaprolactone-epoxide adduct reac
(i) reacting a polycaprolactone polyol having at least tion product mixture is reacted with an inorganic or
two hydroxyl groups in the molecule, a hydroxyl 30 organic base in an amount sufficient to neutralize the
number of from about 15 to about 600 and an aver free carboxyl groups of said adduct reaction product
mixture to produce a water soluble polycaprolactone
age molecular weight of from 290 to about 6000 epoxide reaction product mixture.
with an intramolecular anhydride of a polycarbox k . . . .

35

45

50

55