Reacting methylene and alkene components in presence of tertiary amine reacted with epoxide

A method for reacting a methylene-containing component such as an acrylic polymer prepared from acetoacetoxyalkyl (meth)acrylate and an alkene-containing component such as a polyfumarate, polymaleate, a polyester containing both fumarate and maleate groups or a polyacrylate comprises the reaction of a tertiary amine such as triethylene diamine and an epoxide such as a glycidyl-functional (meth)acrylic polymer in the presence of the methylene-containing component and alkene-containing component. The tertiary amine can be incorporated into the alkene-containing component such as the reaction of an unsaturated polyester with a compound having both tertiary amine and primary or secondary amine groups. The tertiary amine can be incorporated into the methylene-containing component such as an acrylic polymer derived from a tertiary amino-functional monmer and acetoacetoxyalkyl (meth)acrylate. The epoxide can be incorporated into the methylene-containing component such as an acrylic polymer obtained from glycidyl (meth)acrylate and acetoacetoxyalkyl (meth)acrylate. The epoxide can be incorporated into the alkene-containing component.

BACKGROUND OF THE INVENTION 
This invention relates to ambient cure compositions based on the 
base-activated Carbon Michael reaction between active methylene groups and 
active alkene groups. More particularly, the invention is directed toward 
use of tertiary amines and epoxides to activate the Carbon Michael 
reaction. In more specific aspects, the invention is directed toward 
classes of active methylene groups, active alkene groups, tertiary amines 
and epoxides that provide low cost, color and hazard, in two-pack coatings 
with good pot life, cure speed, gloss and durability on exposure to high 
humidity and ultraviolet light. Two-pack aliphatic urethane coatings 
represent the best current technology and provide targets for pot life, 
cure speed, gloss and durability, but alternatives to urethanes are needed 
with advantages in economy, safety, and ease of handling, especially for 
coatings with low levels of volatile solvent. 
Heckles, U.S. Pat. Nos. 4,217,396, 4,217,439, 4,218,515 and 4,229,505 teach 
crosslinked polymers from polyfunctional acrylates and difunctional 
acetoacetates, diacetoacetamides, ureadiacetoacetamides and cyanoacetates 
with diacetoacetoamides and ureadiacetoacetamides. The crosslinking is 
activated by strongly basic catalysts such as sodium methoxide, sodium 
metal, sodium ethylate, and benzyl-trimethyl ammonium methoxide. 
Bartman et al, U.S. Pat. No. 4,408,018 also teaches the use of base 
catalysts with sufficient activity to activate Michael cure reactions, 
such as potassium hydroxide, tetrabutyl ammonium hydroxide, potassium 
amylate, sodium methoxide, potassium ethoxide and other alkali metal 
derivatives of alcohol, and quaternary ammonium bases. However, Bartman et 
al note that amines are generally not sufficiently strong to catalyze the 
Michael reaction between acrylic polymers having pendant acetoacetate 
groups and multifunctional acrylic esters. 
Brindopke et al, Australian Patent No. 8540807-A teaches that strong bases 
such as alkali metal hydroxides or alcoholates cause yellowing and 
cloudiness with the acrylic polymers having pendant acetoacetate groups. 
They specify other active methylene compounds, with activation by 
diazabicyclooctane (triethylenediamine, DABCO); halides of quaternary 
ammonium compounds, especially fluorides; organic phosphonium salts; 
amidines, such as tetramethylguanidine, diazabicycloundecene, and 
diazabicyclononene; phosphanes; alkali metal alcoholates; and quaternary 
ammonium compounds, such as alkylammonium, arylammonium and/or 
benzylammonium hydroxides or carbonates. Brindopke et al also teach that 
these catalysts or catalyst mixtures can be used in the presence of 
tertiary aliphatic amines which in themselves are not active at room 
temperature. Brindopke et al teach use of a broad range of compounds 
having at least two active alkene groups, excluding only those taught by 
Bartman et al. They specifically include derivatives of cinnamic acid, 
crotonic acid, citraconic acid or anhydride, mesaconic acid, fumaric acid, 
dehydrolevulinic acid or sorbic acid, but prefer acrylic acid, methacrylic 
acid and/or maleic acid or anhydride. 
There are problems associated with use of all of the above catalysts for 
cure of those Carbon Michael-Reactive components which are preferred on 
the basis of cost, hazard to users and reactivity at ambient temperature. 
With the components taught by Bartman et al, combining good cure with pot 
life is problematic: at the level of base catalyst required to give good 
ultimate cure, the pot life of the composition is too short. By use of 
quaternary ammonium salts of volatile acids, this problem can be overcome, 
but then combination of early cure and gloss becomes problematic: with 
salts of carbonic acid the surface cure is too fast at levels of catalyst 
giving good ultimate cure, resulting in low gloss from shrinkage due to 
loss of solvent after the surface has crosslinked, while with salts of 
less volatile acids the cure is slower than desired. 
Also, as mentioned by Bartman et al, combination of the required components 
in two stable packages is problematic: bases strong enough to activate the 
cure typically lose activity on extended aging when combined with either 
compositions having pendant acetoacetate groups or compositions having 
other than the most resistant classes of ester bonds. In particular, 
activity is lost on storage of the active base catalyst with acrylic 
polymers containing acetoacetoxyethyl methacrylate (AAEM) and the 
polyacrylate crosslinkers taught in U.S. Pat. No. 4,408,018. This severely 
limits the packaging options: the systems either have three packages, one 
for each component, or one large and one very small package, the small 
package containing the catalyst. It is desired to have only two packages 
of the same order of magnitude in size. 
Similar problems exist when the Carbon Michael-reactive methylene groups 
are esters of acetoacetic acid other than acrylic polymers containing 
acetoacetoxyethyl methacrylate, or when the Carbon Michael-reactive 
methylene groups are esters of malonic or cyanoacetic acid. 
Similar problems exist when the Carbon Michael-reactive alkene component is 
a polyester containing fumarate and maleate moieties. Use of such 
polyesters as alkene component is highly desirable because they are less 
irritating than most multifunctional acrylates, and also because of 
potential for low cost. However, in addition to these pot-life/cure, cure 
rate/gloss, and packaging problems associated with the activators taught 
previously, their utility is problematic for another reason: such 
polyesters give weaker compositions than desired when the Carbon 
Michael-reactive methylene component is low in functionality/molecule. 
When the Carbon Michael-reactive methylene component is high enough in 
molecular weight and active methylene content per molecule for good 
strength and hardness, as with acrylic polymers containing pendant 
acetoacetate moieties, achieving good gloss and durability is problematic, 
probably because of incompatibility or phase-separation between the 
relatively high molecular weight alkene and methylene components. 
Still another problem with polyesters containing fumarate and maleate 
moieties is their susceptibility to hydrolysis. It is known to minimize 
this by use of 2,2-alkylsubstituted 1,3-propanediols as glycols, however 
then polyesters tend to be readily crystallizable with neopentyl glycol 
and expensive with less readily available 2,2-alkylsubstituted 1,3-propane 
diols. 
A solution to the above problems is needed to provide alternatives to 
urethanes for ambient cure, especially for applications requiring exterior 
durability. 
SUMMARY OF THE INVENTION 
It has been discovered that the pot-life/cure, cure rate/gloss and 
packaging problems with preferred alkene-containing and 
methylene-containing components can be overcome by use of tertiary amines 
and epoxides as the main activator of Carbon Michael cure, with a key 
element being the occurrence of most of the reaction between tertiary 
amine and epoxide in the presence of both the activated alkene component 
and the activated methylene component. Without limiting the scope of the 
invention, it is believed that the activation of Carbon Michael cure 
results from the conversion of the tertiary amine to a quaternized 
nitrogen compound via reaction with the epoxy group in the presence of the 
Michael-reactive components. When tertiary amines are mixed with epoxides 
in the absence of Michael-reactive components the typical result is a 
complex mixture of quaternary ammonium compounds, their alkaline 
decomposition products, and polyether moieties from epoxy 
homopolymerization. It is believed that in the presence of activated 
methylene component the reaction between amine and epoxide forms 
quaternary ammonium salts with the weakly acidic methylene component, 
activating the methylene component for reaction with the alkene component. 
Without limiting the scope of the invention, the pot-life/cure problem is 
believed overcome by two fundamental advantages of this method of 
activation. First, the pot-life is extended because the activator 
concentration starts at a low level, and second, the rate of formation of 
activator is greater in the film than in the pot because the 
concentrations of amine and epoxide increase due to loss of solvent. 
Without limiting the scope of the invention, the cure-rate/gloss problem is 
believed overcome by the same mechanism as the pot-life/cure problem. The 
cure rate increases with time as activator is formed from reaction of 
amine and epoxide, allowing solvent to leave the film while it is 
thermoplastic, yet giving a fast cure as sufficient levels of activator 
are formed. 
Since the tertiary amines have much lower alkalinity than alkali or 
quaternary ammonium bases, they can be packaged with components having 
high concentrations of hydrolyzable ester groups, while the alkali or 
quaternary ammonium bases cannot. 
Triethylenediamine does not give sufficient activation of Carbon Michael 
cure in the absence of epoxide. However, in the presence of epoxide, 
triethylenediamine gives faster activation than other tertiary amines, 
which is useful when a fast cure rate is needed. 
The activation by triethylenediamine can in fact be so fast that levels of 
triethylenediamine needed for complete cure give pot lives shorter than 
desired. This problem can be overcome by using a combination of 
triethylenediamine with a another tertiary amine which gives a slower rate 
of activation. Combination of triethylenediamine with other, less volatile 
amines is also preferred for optimum crosslinking of the surface of the 
film to give optimum mar resistance. 
When both the tertiary amine component and the epoxide component are low in 
molecular weight and not selected according to the preferred embodiments 
described below, films prepared using the invention tend to blister when 
exposed to water. This problem is overcome by a variety of solutions 
involving either the amine component or the epoxide component:(1) the 
amine can be incorporated into the active methylene component, for example 
by use of acrylic copolymers that contain both pendant acetoacetate 
moieties and tertiary amine from amine-containing monomers such as 
dimethylaminoethyl methacrylate or dimethylaminopropyl methacrylamide; (2) 
the amine can be incorporated into the alkene component; (3) the epoxide 
can be incorporated into the active methylene component, for example by 
use of acrylic copolymers that contain both pendant acetoacetate moieties 
and epoxide from copolymerization of glycidyl methacrylate, or (4) the 
epoxide can be incorporated into the alkene component. 
A preferred class of amine-containing active methylene components is 
derived from copolymerization of a monomer mixture containing both 
acetoacetate-functional and tertiary amine-functional monomers such as 
dimethylaminoethyl methacrylate or dimethylaminopropyl methacrylamide. The 
level of the tertiary amine-functional monomer is selected according to 
the level of the acrylic polymer in the binder, to provide, along with 
other amine components, the ratios of amine to epoxide specified below. 
The level of tertiary amine-functional monomer then is from about 2 
percent by weight of total monomer for binders with a high level of 
acrylic to 15 percent for binders with a low level of acrylic. 
A preferred class of amine-containing alkene components is derived from 
reaction of alkene components with compounds containing both tertiary 
amine and primary or secondary amine. It is believed that the primary or 
secondary amine reacts with the activated double bonds, giving pendant 
tertiary amine groups. Suprisingly, even though they are of low molecular 
weight, simple compounds containing both tertiary amine and primary amine 
(for example, dimethylaminopropylamine) or both tertiary amine and 
secondary amine (for example, tetramethyliminobis-propylamine), give cure 
and water resistance similar to amine-containing alkene components. 
Without limiting the invention, it is believed that these compounds are 
incorporated into the alkene component during cure, giving compositions 
somewhat similar to those in which they are pre-reacted with the alkene 
component. 
Another preferred class of low molecular weight tertiary amines is Mannich 
reaction products of secondary amine, formaldehyde and phenols, for 
example tris(dimethyl-aminomethyl)phenol. 
The preferred epoxide components contain the epoxide group as glycidyl 
esters, glycidyl ethers, or epoxidation products of alpha olefins. A 
preferred type for economy is the commercial liquid diglycidyl ether of 
bisphenol A, for example EPON 828 from Shell. Other types of epoxide give 
slower cure, presumably because of their slower reaction rate with 
tertiary amines. For best water resistance, especially with low molecular 
weight amine components, the epoxide is incorporated in the 
Michael-reactive methylene or alkene component, for example by use of 
glycidyl methacrylate to give glycidyl esters in an acrylic copolymer 
containing pendant active methylene moieties. However, for economy and 
ease of adjustment of epoxide level, one can use low molecular weight 
glycidyl esters, glycidyl ethers, or epoxidation products of alpha 
olefins. When using the low molecular weight epoxide components, for best 
water resistance it is preferred to use an amine component incorporated 
into the Michael-reactive methylene or alkene component, or capable of 
reaction with one of the Michael-reactive components during cure. 
A preferred method for incorporation of the epoxide in the Michael-reactive 
methylene component is use of acrylic polymers containing pendant 
acetoacetate groups, incorporating epoxide by use of a monomer mixture 
containing glycidyl methacrylate along with acetoacetate-functional 
monomer. The level of glycidyl methacrylate in the acrylic polymer is 
selected according to the level of acrylic polymer in the binder, the 
level of any other acrylic or epoxide components, and the criteria for 
total epoxide level discussed below. With a high level of acrylic polymer 
and all of the acrylic polymer containing epoxide, the glycidyl functional 
monomer may be as low as 4 percent in the acrylic polymer. When both an 
amine-functional acrylic and an epoxy-functional acrylic are used, the 
preferred level of glycidyl methacrylate may be 20 percent or more of the 
acrylic polymer with glycidyl and acetoacetate functionality. 
There are three preferred ways to combine Carbon Michael-reactive, epoxide, 
and amine components to achieve stable packages. The epoxide can be mixed 
prior to use with the active methylene moieties, the Carbon 
Michael-reactive alkene moieties, or a combination of the Michael-reactive 
components. 
The tertiary amine can be mixed prior to use with the active methylene 
moieties or the alkene moieties. When extended package stability is not 
required, the amine can also be mixed prior to use with a combination of 
the Michael-reactive components, but a slow reaction between the 
Michael-reactive components is often activated with this combination. 
A particularly preferred method for achieving two packages of similar size 
is combination of the epoxide with either the active methylene moieties or 
the alkene moieties, and the tertiary amine with the other Carbon 
Michael-reactive component. 
The ratio of total moles of tertiary amine groups to epoxide groups is not 
critical, but is usually from about 0.5 to about 1.5. Since the speed of 
cure increases with concentration of both amine and epoxide groups, and 
the presence of an excess of amine is detrimental to acid resistance and 
weathering resistance, it is preferred to have the ratio of tertiary amine 
groups to epoxide groups from about 0.5 to about 1.0. 
A useful statistic for the activator level is milliequivalents of epoxide 
per 100 grams of all activator and Carbon Michael reactive components, 
based on non-volatile material. This gives a measure of the potential 
moles of strong base per total weight of binder. This number should exceed 
the level of acid in the binder by at least 2 milliequivalents/100 grams. 
When the binder contains low levels of acid, the preferred activator level 
is usually in the range 2-80 milliequivalents per 100 grams, and often in 
the range 10-40, with lower levels giving poor rate of cure and higher 
levels giving adverse effects on water or acid resistance. 
The epoxide/tertiary amine activator can be supplemented by less than about 
10 milliequivalents of preformed strong base per hundred grams of binder, 
with the strong base selected from the group consisting of salts of 
tetramethylguanidine, 1,8-diazabicylo(5.4.0)undec-7-ene, or quaternary 
ammonium hydroxide with carbonic, acetic or hydrofluoric acids and 
mixtures thereof to accelerate cure. The level of strong base should be 
kept to the minimum level giving the desired improvement in early cure, 
due to adverse effects on water resistance. The carbonic salts give the 
best improvement of early surface cure, and are therefore usually 
preferred. This is thought to be due to the ease of loss of acid from the 
film as carbon dioxide. However, even at 10 milliequivalents per hundred 
grams of binder, the carbonic salts tend to give loss of gloss, and thick 
films can even wrinkle due to surface cure exceeding sub-surface cure and 
solvent loss. 
If the level is kept below about 5 milliequivalents of preformed strong 
base, the strong base can be added as hydroxide or free base rather than 
the salt while retaining useful, albeit shortened pot-life. 
To minimize adverse effects on water resistance, it is preferred that the 
hydroxide or salts be selected from tetrabutylammonium, 
tetraethylammonium, and trimethylbenzylammonium. These are commercially 
available as methanolic or aqueous solutions, limiting packaging options 
to those in which the preformed base is kept separate from ester groups. 
Improvement of early cure without the problems of preformed base can be 
accomplished by use of phenols, or combinations of phenols and alcohols. 
Without limiting the scope of the invention, it is believed that phenols 
and alcohols accelerate the reaction between tertiary amines and epoxides. 
Preferred phenols are alkylsubstituted, for example p(t-butyl)phenol and 
nonylphenol. Preferred levels of phenol are about 5 to about 30 
milliequivalents per 100 grams total weight of activator plus Carbon 
Michael-reactive components. The alcohols are used at from 1 to 20 percent 
of the binder, with a preferred alcohol being 2-ethylhexanol. 
Preferred active methylene moieties are esters or amides of acetoacetic 
acid, malonic acid, or cyanoacetic acid. Availability of acetoacetic 
esters or amides via reaction of alcohol or amine groups with diketene 
makes these moieties economically attractive. Malonic ester or amide 
moieties can be preferred for low color with certain alkenes. A 
particularly preferred route to use of malonate moieties is as a polyester 
made by reaction of malonic esters with glycols and other difunctional 
esters or acids. Cyanoacetic esters or amides can be preferred for high 
reactivity with low levels of active methylene functionality per molecule 
or with alkene components that have poor reactivity with acetoacetate or 
malonate moieties. 
Acrylic polymers with pendant active methylene groups are preferred where 
it is desirable to have high levels of active methylene functionality per 
molecule and hard compositions with short tack-free times. For economy and 
ease of synthesis, it is preferred with acrylic polymers to use pendant 
acetoacetate groups, for example by use of allyl acetoacetate, 
acetoacetoxyethyl methacrylate, or acetoacetoxyethyl acrylate as monomers. 
Acetoacetoxyethyl methacrylate or acetoacetoxyethyl acrylate are favored 
for ease of copolymerization, especially when high levels of active 
methylene moiety are desired. The amount of acetoacetate-functional 
monomer is selected to give adequate crosslinking. Higher levels of 
acetoacetate-functional monomer are required as the molecular weight of 
the acrylic polymer is decreased and as the level of the acrylic polymer 
in the binder is decreased. Greater than about 15 percent 
acetoacetate-functional monomer is preferred for solvent resistant 
coatings, with up to about 60 percent being desirable for high solids 
coatings with low molecular weight acrylic polymers or binders having the 
acrylic polymer less than 40 percent of the total weight. 
Acetoacetic, malonic, and cyanoacetic esters and amides of low molecular 
weight mono, di-, tri-, and higher functional alcohols and amines are 
preferred where it is desireable to have solventless ambient cure 
compositions, or as viscosity-reducing components with higher molecular 
weight methylene components. For low color, malonic esters are preferred. 
The alkene component should have at least two alkene groups per molecule. 
Preferred alkene moieties for use with the above methylene components are 
alpha-beta unsaturated esters of acrylic acid, fumaric acid, mixtures of 
fumaric and maleic acid, and the Michael addition products of acrylic acid 
with 1-5 propionate units per double bond. Maleic esters are significantly 
less reactive than fumaric esters. Methacrylate esters are reactive enough 
only with cyanoacetic esters and amides. 
For low color with acetoacetate as active methylene and over a broad range 
of ratios of alkene moiety to active methylene moiety, with molar ratio of 
alkene to methylene as low as 0.9, Michael addition products of acrylic 
acid are preferred as alpha-beta unsaturated acid. The simplest such 
Michael addition product is beta-acryloxypropionic acid. It is preferred 
to use the mixture of beta-acryloxypropionic acid and higher Michael 
addition products, with up to 5 propionate units per double bond, that 
result from reaction of acrylic acid in the presence of catalysts for the 
Oxygen Michael reaction. Without limiting the scope of the invention, it 
is believed that reversal of the Oxygen Michael reaction addition is 
triggered during Carbon-Michael cure when the active methylene content 
drops to a low level, allowing the binder to become more alkaline. The 
reversal of the Oxygen Michael reaction is believed to generate acid, 
preventing the film from becoming strongly alkaline, thus minimizing 
alkali-induced color formation. Although good color can be obtained with a 
variety of such esters, it is preferred for good hardness to use esters of 
a trifunctional alcohol such as trimethylolpropane, and with a molar ratio 
of alkene to active methylene in the range 0.9-2.0. 
With acrylic acid as the alpha-beta unsaturated acid and acetoacetate as 
the methylene moiety, color develops with aging of the cured binder unless 
the ratio of alkene to methylene is greater than 1.5. When the alpha-beta 
unsaturated acrylic esters have three or more alkene groups per molecule, 
the ratio of alkene to active methylene can be as high as 4.0. When the 
alpha-beta unsaturated acrylic esters have only two alkene groups per 
molecule, the molar ratio of alkene to active methylene should be in the 
range 1.5-2.2. 
With fumaric acid or mixtures of fumaric acid and maleic acid as alpha-beta 
unsaturated acid, preferred alkene components are polyesters with a number 
average molecular weight greater than about 500, an equivalent weight less 
than about 700 grams per alkene moiety, and less than about 0.2 
equivalents of acid per 100 grams of polyester solids. Cure is poor 
outside of these ranges, and especially preferred for good cure are 
polyesters with number average molecular weight greater than about 900, 
equivalent weight less than about 500, and less than about 0.1 equivalents 
of acid per 100 grams. The hardest and most chemically resistant films are 
obtained with binders containing lower levels of polyester. For such 
films, it is preferred that the equivalent weight be less than about 300, 
with use of correspondingly low levels of dibasic acids other than 
maleic/fumaric. The least expensive and most flexible films are obtained 
with binders containing higher levels of polyester. For such films it is 
preferred to use a coacid selected as described below. 
For hydrolysis resistance, durability and economy, the polyfunctional 
alcohols used are mixtures of neopentyl glycol, neopentyl glycol 
mono(hydroxypivalate) (ED204), 2,2,4-trimethyl-1,3-pentanediol, 
trimethylolpropane, and cyclohexane dimethanol. Especially preferred are 
mixtures of neopentyl glycol, trimethylolpropane, and neopentyl glycol 
mono(hydroxypivalate). 
A high level of fumaric acid is preferred for reactivity with methylene 
groups, however due to ready crystallizability of fumarate polyesters of 
neopentyl glycol, the preferred ratio of fumaric/maleic is in the range 
from about 80/20 to 20/80. For the best reactivity, the ratio of 
fumaric/maleic should be above 40/60. 
For outdoor durability, it is preferred that the dibasic acid moieties 
other than fumaric and maleic are cycloaliphatic or aliphatic. A 
particularly preferred coacid for hardness and durability is cyclohexane 
dicarboxylic acid. 
For gloss and durability with methylene-functional acrylic polymers, it is 
critical that the acrylic polymer and the polyester form a homogeneous, 
single phase after evaporation of solvent. With neopentyl glycol as main 
glycol and maleic and fumaric acids as main diacids, preferred acrylic 
polymers have 30-50 percent by weight acetoacetoxyethyl methacrylate and 
greater than 30 percent by weight of butyl or isobutyl methacrylate. Such 
acrylic polymers are also compatible with polyesters having substantial 
levels of cyclohexane dicarboxylic acid together with maleic and fumaric 
acids. The film properties can be varied over a wide range while 
maintaining these limits by varying the ratio of the methylene-functional 
acrylic polyer to unsaturated polyester and the equivalent weight of the 
polyester. A given polyester can be used over a range of ratios, however 
it is preferred to have at least 1 alkene group per active methylene group 
for reactivity and less than about 3 alkene groups per active methylene 
groups for durability and early alkali resistance. 
For the best water resistance it is preferred that the end-groups of the 
polyester are hydrophobic rather than hydrophilic alcohol groups. One 
preferred route to such polyesters is use of relatively high-boiling 
monofunctional alcohol in combination with glycols in reaction with 
dibasic acids. This can be done in steps, first preparing an 
acid-terminated polyester, then reducing the acid number to a low value by 
reaction with monofunctional alcohol. A preferred monofunctional alcohol 
is 2-ethylhexanol. A second preferred route is post-reaction of 
hydroxy-terminated polyester with acetic anhydride. A third preferred 
route is post-reaction of hydroxy-terminated polyester with hydrophobic 
isocyanate, with a preferred embodiment for good cure being isocyanates of 
hydroxyalkyl acrylates, which give acrylate-terminated polyesters 
following reaction with the hydroxy-terminated polyester. A fourth route 
is reaction of polyester with an excess of isocyanate, followed by 
addition of monofunctional alcohol. Again a preferred emmbodiment with 
this route is use of a hydroxyalkyl acrylate to give acrylate-terminated 
polyester. A fifth route to such polyesters is preparation from diesters 
and glycols by transesterification. 
With hydroxyl-terminated polyesters, hardness and chemical resistance can 
be improved by adding multifunctional isocyanate at the time of mixing 
Carbon Michael-reactive components, tertiary amine and epoxide. 
DETAILED DESCRIPTION OF THE INVENTION 
The present invention relates to an improved method for activating Carbon 
Michael cure with combinations of Carbon Michael-reactive active methylene 
compounds and Carbon Michael-reactive alkene compounds preferred for 
reactivity, economy, low hazard and low color. 
The invention also relates to coating or binder compositions including 
active methylene moieties, Michael-reactive alkene groups, epoxide groups, 
tertiary amines and supplementary additives for improvement of early cure. 
The abbreviations used in the Examples are as follows: 
______________________________________ 
AAEM Acetoacetoxyethyl methacrylate 
BA Butyl acrylate 
bis-DMAPA bis-Dimethylaminopropyl amine 
(tetramethyliminobispropylamine) 
BMA Butyl methacrylate 
ButAc Butyl acetate 
Capr Capryl alcohol 
DBM Dibutylmaleate 
DBUACETATE Diazabicycloundecene acetate 
DBUCARB Diazabicycloundecene carbonate 
DMAEMA Dimethylaminoethyl methacrylate 
DMAM Dimethylaminomethy1l-substituted phenol 
DMAPA Dimethylaminopropyl amine 
DMAPMA Dimethylaminopropyl methacrylamide 
DMCD Dimethyl ester of cyclohexane dicarboxylic acid 
DMM Dimethylmaleate 
EthH 2-Ethylhexanol 
GMA Glycidyl methacrylate 
HEMA Hydroxyethyl methacrylate 
HOAC Acetic Acid 
IBMA Isobutyl methacrylate 
MAA Methacrylic acid 
MAnh Maleic anhydride 
meq Milliequivalent 
MMA Methyl methacrylate 
NPG Neopentyl glycol 
Sty Styrene 
TBACARB Tetrabutylammonium bicarbonate 
TBAH Tetrabutylammonium hydroxide 
TEDA Triethylenediamine 
TMGACETATE Tetramethylguanidine acetate 
TMGCARB Tetramethylguanidine bicarbonate 
TMPAcAc Trimethylolpropane trisacetoacetate 
TMPAOPATE Trimethylolpropane tris(aopate), Mn = 570. 
TMPMal Trimethylolpropane tri(ethyl malonate) 
TMPTA Trimethylolpropane triacrylate 
Xyl Xylene 
______________________________________

EXAMPLE 1 
Preparation of Polyester A, an Alkene-Containing Component Having a Low 
Fumarate/Maleate Ratio 
A 1000 ml. four-necked flask equipped with a thermometer, subsurface 
nitrogen ebullator, mechanical stirrer, 6' Vigreux column and strip 
condenser was charged with 360 g. dimethyl maleate (2.5 moles), 117 g. 
neopentyl glycol (1.125 moles), 148.5 g 2,2-Diethyl-1,3 propanediol (1.125 
moles), 1.2 g. dibutyltin oxide and 0.1 g. phenothiazine. The resulting 
slurry was heated rapidly, under nitrogen, to 160 degrees C. to dissolve 
the diols and initiate the transesterification reaction. Methanol 
generated in the process was removed by fractional distillation through 
the Vigreux column. The mixture was kept 2 hours at 160 degree C. and then 
was heated gradually to 210 degrees C. over a period of 5-6 hours. 
Approximately 90% of the theoretical alcohol was collected. After a 1 hour 
hold, the resin was stripped of volatiles in vacuo (15 min., 30-40 mm.), 
allowing the temperature to decrease to 175-180 degrees C. The polyester 
was cooled to 140 degrees C. and then diluted with xylene to afford the 
finished product at 83.8% solids, viscosity 4800 cps. The fumarate/maleate 
ratio estimated from an NMR spectrum was 11/89. Gel permeation 
chromatography indicated that the molecular weights were Mw=2010 and 
Mn=1320. 
EXAMPLE 2 
Preparation of Polyester B, an Alkene-Containing Component having a High 
Fumarate/Maleate Ratio 
Polyester B was prepared from polyester A by isomerization with 0.7 wt. % 
di-n-butylamine, giving a fumarate/maleate ratio estimated by NMR of 
90/10. The solids content was 84.6 percent, and the viscosity was 14,100 
cps. Gel permeation chromatography indicated that the molecular weights of 
Polyester B were Mw=2390, Mn=1450. 
EXAMPLE 3 
Preparation of Acetoacetate Functional Polymer A, a Methylene-Containing 
Component 
Three hundred twenty (320) grams of reagent grade xylene solvent was 
weighed into a one liter four neck flask. A monomer mix was prepared from 
96 grams methyl methacrylate, 96 grams butyl methacrylate, 96 grams 
styrene, 192 grams AAEM, and 7.2 grams of t-butyl peroctoate. A solution 
of n-dodecyl mercaptan was prepared by dissolving 12.1 grams of the 
mercaptan in enough of the solvent to make 60 ml of solution. The 
remaining solvent was stirred with a nitrogen sparge and heated to 105 
degrees C. The monomer mix and mercaptan solution were then added 
simultaneously over a period of 95 minutes at 103-106 degrees C. Following 
completion of the additions the mixture was held at 105 degrees C. for 
another 150 minutes with 2 gram portions of t-butyl peroctoate being added 
after 45 and 95 minutes. The resulting 816 grams of solution was found to 
contain 60.9 wt. % polymer solids. Gel permeation chromatography indicated 
that the molecular weights were Mw=15,200, Mn=5560. The monomer ratio was 
40 AAEM/20 MMA/20 BMA/20 Styrene. The initiator was 1.5% t-butyl 
peroctoate on polymer solids. The chain regulator was 2.5% n-dodecyl 
mercaptan on polymer solids. 
EXAMPLE 4 
Preparation of Acetoacetate Functional Polymer B, a Second 
Methylene-Containing Component Having a Lower Molecular Weight 
Polymer B was prepared by the same procedure used with Polymer A, except 
for use of 1.5% 2,2'-azobis(2-methylbutanenitrile) as the initiator in 
place of t-butyl peroctoate, and use of 5.0% n-dodecyl mercaptan in place 
of 2.5%. Gel permeation chromatography indicated that the molecular 
weights were Mw=8170, Mn=2720. 
EXAMPLE 5 
White Paints Demonstrating Pot Life/Cure and Gloss/Cure Problems with 
Tetrabutylammonium Hydroxide as Activator 
In this example, a preformed strong base activator component believed to be 
the best activator of the prior art, tetrabutylammonium hydroxide, was 
used. This example demonstrates fumarate gives unexpectedly superior 
results, even with an activator of the prior art. It also demonstrates the 
cure/gloss problem and demonstrates the pot life cure problem. 
Pigment grinds were prepared using Titanium Dioxide as pigment with a high 
speed disperser, grinding the pigment in the acetoacetate functional 
polymers A and B. Eight and nineteen hundreths grams of pigment grind 
containing 3.75 grams pigment, 2.50 grams polymer solids, and 1.94 grams 
xylene were mixed with additional acetoacetate polymer (3.31 grams 
solids), 2.13 grams xylene, and alkene component. The alkene components 
used were Polyester A (Maleate), Polyester B (Fumarate), and TMPAOPATE 
(trimethylolpropane tris(acryloxypropionate, the ester of 
trimethylolpropane with acrylic acid Michael addition products, having 
three moles of alkene per 570 grams). The weight of alkene component 
solids in each case was 2.94 grams, giving close to 1.5 equivalents of 
alkene component per mole of AAEM in the acrylic. Since earlier work 
indicated that addition of butanol could lengthen pot life and improve 
gloss, the level of butanol was studied in addition to the level of 
catalyst, molecular weight of the AAEM polymer, and type of alkene 
component. The paints were completed by adding xylene or xylene and 
butanol to give 58-60 weight percent solids after catalyst addition and 0 
or 25 weight percent butanol on binder solids, then finally adding 0.35, 
0.52, or 0.78 grams of 31 wt. % tetrabutylammonium hydroxide in methanol, 
giving 4.8, 7.2 or 10.8 mmoles quaternary nitrogen/100 grams binder solids 
(1.25, 1.87, or 2.80 wt. % catalyst solids on binder solids). 
The catalyst was added last, after obtaining a homogeneous mixture of the 
other components. Then the paint was mixed further for two minutes and 
drawn with a 4-mil gate on phosphatized cold rolled steel (Bonderite 1000 
pretreated steel). Measurements were made of time to freedom from tack 
with a Zapon tack tester and a 500 gram weight, and of time to gelation of 
the remaining paint. Two panels were drawn with each paint. One panel was 
aged at ambient for two days, then held for three days in an oven at 140 
degrees F., then two days at ambient. At this time the gloss (20 degree) 
and Knoop Hardness were measured. The other panels were aged under ambient 
conditions. At 28 days with the set of panels using Acetoacetate 
Functional Polymer A and at 26 days with the set of panels using 
Acetoacetate Functional Polymer B, the Knoop Hardness was measured and 
also the response of the film to a spot of xylene, which was placed on the 
film and allowed to evaporate. The spot was rated for blistering using the 
ASTM blister size and frequency standards and for degree of soluble 
material at the perimeter of the spot, on a scale from very slight 
(VSlight) to severe. 
Results are tabulated in Table 1. At the lowest catalyst levels and with 
the least reactive (low molecular weight acrylic copolymer, maleate as 
alkene component) systems, the gloss and pot-life are promising, but the 
cure is poor. At the higher catalyst levels, cure improves, but gloss and 
pot-life are poor. 
In contrast to the teaching of Brindopke et. al., fumarate polyesters give 
better cure than maleate polyesters. 
TABLE 1 
__________________________________________________________________________ 
Demonstration of pot life/cure and gloss/cure problems with Example 5 
activator and 
discovery of reactivity advantages for fumarate over maleate polyesters. 
500 gm. 
% Wt. 
Amt. Cat. 
Gel Time 
Zapon Tack 
Gloss Hardness 
Hardness 
Xylene Spot 
Polyester 
Butanol 
(meq/100 g) 
(mins.) 
(mins.) 
(After Oven) 
(After Oven) 
(After 28 Days) 
(After 28 
__________________________________________________________________________ 
Days) 
ACETOACETATE FUNCTIONAL POLYMER A 
(High Mol. Wt.) 
A 0 4.8 429-1372 
191-234 
81.0 1.7 0.8 Severe 
A 0 7.2 306-329 
228-232 
73.0 3.0 1.4 Mod/Sev 
A 0 10.8 241-277 
176-221 
67.6 5.6 1.9 Moderate 
A 25 4.8 1347 167-214 
79.5 1.7 1.0 9DBlist 
A 25 7.2 400-1340 
160-210 
57.6 2.8 1.3 Severe 
A 25 10.8 389-1328 
149-199 
72.0 6.0 1.9 Moderate 
B 0 4.8 54-80 133-184 
61.0 9.2 2.8 Moderate 
B 0 7.2 4-36 72-87 26.1 11.8 3.7 Slt/Mod 
B 0 10.8 4-26 46-62 9.6 14.2 6.6 VSlight 
B 25 4.8 135-153 
99-114 
67.0 9.0 2.9 Mod/Sev 
B 25 7.2 53-65 57-74 55.1 13.4 5.7 Moderate 
B 25 10.8 4-45 &lt;50 46.7 14.3 6.5 Slight 
TMPAOPATE 
25 4.8 &gt;1056 &gt;1054 81.0 2.4 2.2 Moderate 
TMPAOPATE 
25 7.2 102-1050 
198-1048 
61.8 6.7 4.5 VSlight 
TMPAOPATE 
25 10.8 67-82 46-60 52.1 10.7 5.3 VSlight 
ACETOACETATE FUNCTIONAL POLYMER B 
(High Mol. Wt.) 
A 0 4.8 470-4304 
487-4320 
80.2 0.8 0.6 9FBlist 
A 0 7.2 465-4298 
481-4320 
82.0 1.3 0.8 9MDBlist 
A 0 10.8 449-4281 
286-335 
71.9 1.9 1.0 9MBlist 
A 0 16.2 &gt;4274 4248-279 
62.7 4.6 1.4 Severe 
A 25 4.8 &gt;4274 451-4320 
74.7 0.8 0.7 9FBlist 
A 25 7.2 &gt;4256 405-435 
77.8 1.3 0.9 9MDBlist 
A 25 10.8 &gt;4251 302-335 
62.5 2.0 1.0 9MBlist 
A 25 16.2 &gt;4242 211-245 
73.5 5.0 1.6 Severe 
B 0 4.8 85-89 329-352 
71.3 4.6 1.9 9MBlist 
B 0 7.2 38-49 160-204 
46.5 9.5 3.2 Mod/Sev 
B 0 10.8 33-43 88-127 
12.0 12.8 4.7 Moderate 
B 25 4.8 199-4036 
177-203 
75.5 4.5 2.2 9MBlist 
B 25 7.2 92-95 170-193 
65.4 8.7 3.8 Mod/Sev 
B 25 10.8 51-56 140-164 
63.6 12.1 5.1 Moderate 
TMPAOPATE 
25 4.8 &gt;4030 180-4320 
67.8 1.3 1.3 Moderate 
TMPAOPATE 
25 7.2 144-3966 
146-4320 
37.9 3.7 3.1 Slt/Mod 
TMPAOPATE 
25 10.8 42-134 
51-92 39.7 8.4 3.6 VSlight 
__________________________________________________________________________ 
EXAMPLE 6 
AAEM Copolymers C, D and E (20 AAEM, Higher Molecular Weight) 
AAEM copolymers were prepared as described above except no mercaptan was 
used, the initiator was 2.16 wt. % t-butyl peroctoate on monomers, and the 
monomer compositions were as follows: 
AAEM copolymer C: 40 MMA/20 BA/20 Sty/20 AAEM 
AAEM copolymer D: 35 MMA/20 BA/20 Sty/20 AAEM/5 DMAEMA 
AAEM copolymer E: 38 MMA/20 BA/20 Sty/20 AAEM/1.5 DMAEMA/0.5 MAA. 
Gel permeation chromatography indicated the following molecular weights: 
C-Mw=35,000, Mn=13,900; D-Mw=49,700, Mn=15,100; E-Mw=43,300, Mn=16,000. 
EXAMPLE 7 
Effect of Epoxy Resin on Cure of AAEM Copolymers C, D and E with TMPAOPA in 
White Paints 
Grinds of titanium dioxide were prepared in the AAEM copolymers using a 
high speed disperser as above. Weights of grinds giving 6.01 grams polymer 
solids and 3.10 pigment were mixed with 1.51 grams TMPAOPA. This weight 
ratio gave 1.5 moles of alkene per mole of acetoacetate. One and 
eighty-eight one hundredths grams of n-butanol and sufficient xylene were 
added to make the paints 60 wt. percent solids after addition of 
activating additives. One set of paints contained 0.61 grams of epoxy 
resin DER-732 (a trademark of Dow), a polyglycol diglycidyl ether 
(alkylene oxide glycol type) with 305-335 epoxy equivalents per gram. This 
level of epoxy resin gave a 1/1 equivalent ratio between epoxy and 
tertiary amine in the case where the copolymer contained 5% DMAEMA. 
All paints contained 0.58% choline based on binder solids, giving 4.8 
mmoles quaternary ammonium/100 grams of binder. This level had given 
marginal cure in earlier experiments without epoxy added. The choline was 
added last, with the epoxy added as the final component in the mixes made 
prior to adding the choline. Viscosities of the paints were measured 2 
minutes after adding the choline, and the paints were then drawn on 
phosphatized cold rolled steel (Bonderite 1000) panels using a 4 mil gate. 
Results are shown in Table 2. 
TABLE 2 
______________________________________ 
Effect of combination of tertiary amine and epoxy on cure. 
Sample Number 1 2 3 4 5 6 
______________________________________ 
Copolymer A B C A B C 
DMFMA level in 
None 5% 1.5% None 5% 1.5% 
copolymer 
MAA level in copolymer 
None None 0.5% None None 0.5% 
Epoxy Resin Added 
Yes No 
Viscosity at 2 minutes (cps) 
176 220 178 204 278 212 
Viscosity at 100 minutes 
334 254 178 204 320 224 
Viscosity at 300 minutes 
Gel 400 192 Gel 400 224 
Viscosity at 3 days Gel 258 Gel 258 
Minutes to pass 500 g 
265- &gt;433 &gt;433 75- 164- 280- 
Zapon Tack-Free 
281 83 189 299 
Film Properties after 13 
days Ambient Cure 
20 Degree Gloss, Panel A 
77.1 83.8 83.9 70.5 82.3 86.0 
20 Degree Gloss, Panel B 
78.5 84.5 84.2 72.2 82.9 86.5 
Knoop Hardness 
0.95 8.59 2.16 2.30 2.17 1.20 
Pencil Hardness 
HB 2H F F F HB 
Pencil after 10 sec. MEK 
&lt;6B 2H &lt;6B &lt;6B &lt;&lt;6B &lt;&lt;6B 
Xylene Spot Attack 
Severe Slight Mod. Mod. Mod. Mod. 
______________________________________ 
(Mod. = Moderate) 
Sample 2, combining 5% tertiary amine in the AAEM copolymer with a 
stoichiometric amount of added epoxy, has dramatically better film 
properties, combining good gloss and solvent resistance. In the absence of 
added epoxy, amine detracts from cure, and in the absence of amine in the 
copolymer epoxy detracts from cure. 
EXAMPLE 8 
Comparison of Epoxy Resins for Cure with No Added Strong Base 
Clear enamels were prepared with an AAEM copolymer having composition 40 
AAEM/15 MMA/20 BMA/20 Sty/5 DMAEMA and a polyester crosslinker prepared 
from (mole ratios): 
3.0 Maleic Anhydride/2.0 Trimethylpentanediol/2.0 NeopentylGlycol. 
The enamels were prepared at 51 wt. % solids with xylene as sole solvent. 
Epoxy resins were added to give a 1/1 equivalent ratio between amine and 
epoxy. The weight ratio of AAEM copolymer solids/polyester solids was 
668/332, giving 1.5 equivalent C.dbd.C/acetoacetate. 
All of the enamels had extended pot life, gelling only after three or more 
days. Table 3 shows film hardness results. 
TABLE 3 
______________________________________ 
Hardness development with only epoxy/amine latent catalyst. 
Knoop Hardness 
Epoxy 14 
Identification 
Chemical Composition 
1 day 8 day 
day 
______________________________________ 
Araldite RD-1 
Butyl Glycidyl Ether 
0.32 0.69 0.82 
Araldite CY-179 
Cycloaliphatic Diepoxide 
0.38 0.52 0.59 
Araldite DY-025 
C-12/C-14 Alkyl Glycidyl Ether 
tacky 5.77 9.90 
Araldite DY-027 
C-8/C-10 Alkyl Glycidyl Ether 
0.36 3.28 7.06 
Araldite MY-720 
N-Tetraglycidylmethylenbis- 
0.34 1.54 5.72 
benzenamine 
Araldite Resin 
4-Glycidyloxy-N,N-di-Glycidyl 
0.32 5.20 9.65 
500 aniline 
Araldite Resin 
Same as Resin 500 0.38 4.54 9.72 
510 
Heloxy MK-116 
2-Ethylhexyl Diglycidyl Ether 
0.36 4.38 9.24 
Heloxy WC-67 
1,4-Butanediol Diglycidyl Ether 
0.32 9.54 12.55 
Heloxy WC-68 
Neopentylglycol Diglycidyl 
0.33 9.18 11.85 
Ether 
Heloxy MK-107 
Cyclohexyldimethanol Diglyc. 
0.32 8.86 12.35 
Ether 
Heloxy WC-69 
Resorcinol Diglycidyl Ether 
0.31 9.80 13.00 
Heloxy WC-84 
Aliphatic Polyol Di/Triglyc. 
tacky 2.88 5.97 
Ether 
Epon 828 Bisphenol A Digylcidyl Ether 
0.39 9.82 14.40 
______________________________________ 
With the exception of butyl glycidyl ether and the cycloaliphatic 
diepoxide, all of the epoxy-functional compounds gave good hardness 
development. 
EXAMPLE 9 
Cure with No Strong Base Added, Comparing Triethylenediamine with 
Dimethylaminomethyl-Substituted Phenol and Amine in the AAEM Copolymer, at 
Various Levels of Epoxy Resin 
Clear enamels were prepared using either an AAEM copolymer that did not 
have amine comonomer, with a composition 50 IBMA/10 Styrene/40 AAEM or a 
related composition containing dimethylaminopropyl methacrylamide 
(DMAPMA): 50 IBMA/5 Styrene/40 AAEM/5 DMAPMA. The crosslinker was a 
polyester prepared from (mole ratio) 5 diethyl fumarate/4 2-methyl, 
2-propyl, 1,3-propanediol. Neopentyl diglycidyl ether was used as the 
epoxy. The enamels with the resin without amine were formulated with 
triethylenediamine (TEDA) or dimethylaminomethyl-substituted phenol (DMAM) 
at 21, 42 or 63 meq amine nitrogen per 100 grams of binder. The epoxy was 
added at various levels relative to the amine. The enamels were drawn on 
phosphatized cold-rolled steel (Bonderite 1000) with an applicator having 
a 4 mil gate one hour after mixing. Results are shown in Table 4. 
TABLE 4 
__________________________________________________________________________ 
Evaluation of TEDA and DMAM as tertiary amine for latent 
catalyst system with epoxides. 
Amine Epoxy 
Gel 500 g Knoop Pencil 
Butyl 
Level Level 
Time 
Zapon Hardness 
Hardness 
Acetate 
Amine (meq/100 grams) 
(Hrs) 
(Minutes) 
1 day 
14 day 
14 day 
Patch 
__________________________________________________________________________ 
Enamels using AAEM copolymer without copolymerized amine. 
DMAM 21 21 &gt;120 
344-382 
0.36 
9.97 
F &lt;6B 
DMAM 42 42 &gt;120 
514-1419 
0.76 
15.50 
H &lt;6B 
DMAM 63 63 98-120 
521-1416 
1.76 
13.95 
H HB 
DMAM 42 84 98-120 
518-1409 
1.20 
13.1 
H HB 
DMAM 42 126 76-98 
514-1405 
1.52 
12.35 
H HB 
DMAM 21 63 &gt;120 
511-1406 
0.58 
11.10 
F &lt;6B 
TEDA 21 21 10-24 
180-274 
3.72 
13.33 
F No Film 
TEDA 42 42 &lt;5 172-270 
5.52 
12.75 
F &lt;6B 
TEDA 63 63 &lt;5 173-267 
6.74 
12.65 
H B 
TEDA 42 84 &lt;5 312-348 
3.49 
13.27 
H &lt;6B 
TEDA 42 126 &lt;5 161-266 
2.06 
7.95 
F &lt;6B 
TEDA 21 63 &lt;5 408-456 
1.99 
8.36 
F &lt;6B 
Enamel using AAEM copolymer with copolymerized amine. 
DMAPMA 
21 21 &gt;120 
404-452 
0.33 
11.43 
H &lt;6B 
__________________________________________________________________________ 
TEDA was the only amine tested that gave an early cure comparable to added 
strong base. 
The experiment suggests that for the best combination of pot life, early 
cure and ultimate properties a combination of TEDA with less rapidly 
reacting tertiary amines is preferred. 
EXAMPLE 10 
Experiment Comparing Combinations of Tertiary Amines 
Enamels were prepared using a different pair of related AAEM copolymers 
with and without copolymerized amine: 
AAEM resin A: 20 BMA/20 MMA/20 Styrene/40 AAEM. 
AAEM resin B: 20 BMA/15 MMA/20 Styrene/40 AAEM/5 DMAEMA. 
The crosslinker was a polyester made from (mole ratios): 7.35 Neopentyl 
Glycol/1.0 Isophthalic Acid/1.0 Terephthalic Acid/4.0 Maleic 
Anhydride//2.0 Diethyl Fumarate. The crosslinker was used at a level 
giving one equivalent of C.dbd.C/acetoacetate (a weight ratio of about 
67.5/32.5 AAEM copolymer/polyester solids). Films were drawn with a number 
of combinations of amine components, with the epoxy level adjusted to give 
one epoxy equivalent/equivalent of amine nitrogen except in one case with 
tertiary amine in the polymer and no added amine. Films were drawn as in 
the above experiments. The epoxy was neopentyl diglycidyl ether. The 
results are shown in Table 5. 
TABLE 5 
__________________________________________________________________________ 
Comparison of combinations of amine components with epoxy 
addition at 1 equivalent epoxy/tertiary amine. 
Amines and 
Quat. Added Patch Test 
Haze 
AAEM 
(Type/eqvs. 
Epoxy 
Knoop Hardness 
Pencil 
17 day in 
Resin 
per 100 gr.) 
eqvs. 
1 day 
7 day 
17 day 
17 day 
ButAc 
Xyl Humid. 
__________________________________________________________________________ 
A None None 
0.3 
1.0 
1.4 3B Soluble 
Soluble 
Heavy 
A TBACARB/5 
None 
1.2 
2.7 
3.5 F &lt;6B &lt;6B Slight 
A TEDA/10 
10 0.9 
5.6 
6.7 F &lt;6BWrnkl 
&lt;6B Moder. 
A TEDA/20 
20 2.3 
8.0 
8.6 F &lt;6BBlstr 
&lt;6BBlstr 
Moder 
A TEDA/10+ 
20 1.3 
8.0 
10.7 
F &lt;6B &lt;6B Moder. 
B None None 
0.5 
1.1 
1.6 B Soluble 
Soluble 
Heavy 
B TBACARB/5 
20 1.2 
7.8 
11.9 
H &lt;6B &lt;6B Moder. 
B TEDA/10 
30 1.0 
9.0 
11.5 
F &lt;6B &lt;6B None 
B TEDA/5 25 0.8 
8.2 
12.1 
F &lt;6B 2B None 
__________________________________________________________________________ 
*AAEM Resin A without copolymerized amine, Resin B has 5% DMAEMA. 
*TBACARB = Tetrabutylammonium bicarbonate. 
(B) = Blistered 
(W) = Wrinkled 
With the AAEM resin having no copolymerized amine, the combination of TEDA 
and DMAM gave better film properties at 17 days than TEDA alone at the 
same level of nitrogen. 
The best properties were with the combination of copolymerized tertiary 
amine and TEDA. 
EXAMPLE 11 
Heat Aging of TEDA with AAEM Copolymer 
In Column 4 (Examples 13 and 14) of U.S. Pat. No. 4,408,018, reference is 
made to loss of crosslinking activity on aging strong base catalysts with 
AAEM copolymer for 10 days at 140.degree. F., a typical package stability 
test condition. It has been shown in the preceding examples that with 
triethylenediamine plus epoxy one can achieve speed of cure needed for 
ambient cure coatings and with combinations of triethylenediamine and 
other tertiary amines one can achieve this in combination with good pot 
life and film properties. A heat stability test was conducted to determine 
if the crosslinking activity was stable. The AAEM copolymer and 
crosslinker were: 50 IBMA/10 Styrene/40 AAEM and 5 Diethyl Fumarate/4 
2-methyl, 2-propyl, 1,3-propanediol. Clear enamels with a 1/1 ratio of 
C.dbd.C/acetoacetate were used. Mixtures of TEDA and AAEM copolymer heat 
aged at 140.degree. F. for 10 days were compared with freshly prepared 
mixtures by combination with crosslinker and epoxy and comparison of 
tack-free time and hardness development of films and viscosity progression 
of enamels. No loss of crosslinking activity was observed when TEDA was 
heat-aged with the AAEM copolymer at levels giving 21, 43, or 64 
milliequivalents of nitrogen. 
EXAMPLE 12 
Preparation of Pigment Grinds for Deep-Tone Blue Paints 
Pigment dispersions for the paints were prepared in AAEM copolymer 
solutions by a sand mill procedure, using the following ratio of 
materials: 180 grams AAEM copolymer solids/34.63 grams Phthalocyanine Blue 
pigment (BT-4170, DuPont)/85.37 grams titanium dioxide (Ti-Pure R-960, 
DuPont)/200 grams xylene. The AAEM copolymers were at about 60 percent 
solids in xylene, with additional xylene added as required (to give 200 
grams), based on the exact solids of the copolymer. 
EXAMPLE 13 
Comparison in Blue Paints of Binder Based on Combination of AAEM/GMA/BMA 
and AAEM/DMAPMA/BMA Copolymers with TEDA with Binder Based on AAEM/MMA/BMA 
Copolymer and Tetrabutylammonium Carbonate, Using Fumarate Polyester as 
Alkene Component. 
The AAEM copolymers were prepared without mercaptan chain transfer agent, 
with the following monomer compositions and molecular weights (Mw/Mn) 
indicated by gel permeation chromatography: 
AAEM Copolymer F: 40 AAEM/20 GMA/40 BMA (Mw/Mn=16,700/6620) 
AAEM Copolymer G: 40 AAEM/10 DMAPMA/50 BMA (Mw/Mn=10,600/4080) 
AAEM Copolymer H: 40 AAEM/5 MMA/55 BMA (Mw/Mn=14,800/6550). 
The polyester was prepared with the following mole ratios of components: 
0.67 trimethylolpropane/4.51 neopentyl glycol/2 maleic anhydride/3 diethyl 
fumarate/2 dimethyl cyclohexanedicarboxylate. The molecular weights 
(Mw/Mn) indicated by gel permeation chromatography were 9250/1750. The 
ratio of fumaric to maleic indicated by NMR was 87/13. 
The paints were prepared by mixing pigment grind, additional AAEM 
copolymer, polyester, xylene, and a silicone leveling aid (SF-1023, 
General Electric Co.) at 0.1 weight percent of binder solids to give a 
homogeneous mixture. Then TEDA or tetrabutyl ammonium bicarbonate was 
added. All paints were 54.5 weight percent solids when complete and 
contained 0.364 grams Phthalocyanine Blue and 0.897 grams titanium dioxide 
per 10 grams binder. The TEDA was added as a 15 percent solution in methyl 
ethyl ketone. The tetrabutyl ammonium bicarbonate was prepared by 
carbonation of tetrabutylammonium hydroxide in methanol, and was 19.4 
weight percent in methanol (0.64 meq/gram solution by titration). The TEDA 
level was 20 meq/100 grams binder (1.1 weight percent). The 
tetrabutylammonium bicarbonate level was 7.5 meq/100 grams binder. The 
ratio of AAEM copolymer/polyester solids was 2/1, giving 1 mole of 
alkene/mole of acetoacetate. With the system using AAEM copolymers F and 
G, the weight ratio of F/G was 1/1. 
Paints were drawn with a 4 mil gate on phosphatized steel panels (Bonderite 
1000) and on glass panels. The paint with tetrabutylammonium bicarbonate 
gave a pale blue, indicating flocculation of pigment. The paint with TEDA 
gave the desired deep-tone blue. 
Table 6 shows film properties after ambient aging: Knoop and Pencil 
Hardness, impact resistance and gloss measured with the steel panels and 
volumetric swell ratio in butyl acetate measured with film lifted from the 
glass panels. The swell ratio measurement was based on increase in length 
of a 3 cm piece of film on swelling with butyl acetate, and calculated as 
the cube of the swelled length divided by the original length. 
TABLE 6 
______________________________________ 
Blue paint comparison of activation by tetrabutylammonium 
bicarbonate and by epoxide/tertiary amine with polyester as 
alkene component. 
AAEM Copolymer F/G (1/1) H 
______________________________________ 
Additive TEDA TBACARB 
Blueness Deep Pale 
Knoop Hardness at 1 day 
1.6 1.3 
Knoop Hardness at 4 days 
4.5 1.5 
Knoop Hardness at 14 days 
8.9 2.4 
Pencil Hardness at 1/4/14 days 
B/F/H B/B/B 
Swell ratio at 4/14 days 
1.73/1.55 2.04/2.00 
Direct Impact (in-lb) at 14 days 
70-90 50-70 
20 degree gloss at 14 days 
81.2 66.0 
______________________________________ 
The activator system of the invention shows much better development of 
hardness and combines excellent mechanical properties and solvent 
resistance with excellent gloss, while the preformed strong base activator 
gives marginal hardness and solvent resistance and poor gloss. The 
preformed strong base also causes a pigment flocculation. 
EXAMPLE 14 
Comparison in Blue Paints of Binder Based on Combination of AAEM/GMA/BMA 
and AAEM/DMAPMA/BMA Copolymers with TEDA with Binder Based on AAEM/MMA/BMA 
Copolymer and Tetrabutylammonium Carbonate, Using TMPAOPA as Alkene 
Component 
The AAEM copolymers were F, G, and H described in Example 13. The paints 
were prepared as described in the Example 13, with the only difference 
being the ratio of AAEM polymer/alkene component, which was 745/255, again 
giving a 1/1 mole ratio of alkene groups to acetoacetate groups. 
Table 7 shows film properties obtained as described in Example 13. The 
paint with tetrabutylammonium bicarbonate was pale like in the preceding 
example. The paint with TEDA was slightly less deep a blue than the 
corresponding paint with polyester. 
TABLE 7 
______________________________________ 
Blue paint comparison of activation by tetrabutylammonium 
bicarbonate and by epoxide/tertiary amine with TMPAOPA as 
alkene component. 
______________________________________ 
AAEM Copolymer F/G (1/1) H 
Additive TEDA TBACARB 
Blueness Nearly Pale 
Deep 
Knoop Hardness at 1 day 
4.1 1.3 
" 4 days 7.2 1.8 
" 14 days 10.0 2.7 
Pencil Hardness at 1/4/14 days 
F/F/H F/HB/HB 
Swell ratio at 4/14 days 
1.41/1.34 1.58/1.54 
Direct Impact (in-lb) at 14 days 
70-90 &gt;130 
20 degree gloss at 14 days 
82.9 79.1 
______________________________________ 
The properties with tetrabutylammonium bicarbonate activator were better 
with TMPAOPA as alkene component than with polyester (Example 13), but the 
activator system of the invention again shows superiority in hardness 
development, solvent resistance, gloss and color. 
EXAMPLE 15 
Preparation of Ethylhexyl Terminated Polyester C 
A 1000 ml. four-necked flask equipped with thermometer, nitrogen sparge 
tube, overhead mechanical stirrer and Barrett trap above a six inch 
Vigreux column was charged with 44.3 g. trimethylolpropane (0.33 mol), 
103.1 g. neopentyl glycol (0.99 mol), 194.2 g. maleic anhydride (1.98 mol) 
and 0.9 g. triphenyl phosphite. The resulting mixture was stirred with a 
nitrogen sparge and heated to approximately 130.degree. C. At this point 
all of the solids melted and an exothermic reaction rapidly increased the 
temperature of the mixture to 180.degree. C. Xylene was added through the 
condenser until the solution refluxed vigorously at a pot temperature of 
180.degree. C. Refluxing at that temperature was continued for two hours 
during which 18 ml. of aqueous distillate was collected in the Barrett 
trap. The mixture was then allowed to stand at room temperature overnight. 
The following day 130.2 g. 2-ethyl-1-hexanol (1.00 mol) and 1.8 g. 
dibutyltin oxide were added. The mixture was reheated, again under 
nitrogen, and refluxed at 190.degree. C. for an additional 8 hours during 
which time approximately 16.5 ml. of water was collected in the trap. The 
course of the reaction was followed by periodically removing samples of 
the reaction mixture and titrating them with base to determine the amount 
of unesterified acid remaining. At the end of the reaction, the acid titer 
was 0.027 meq/g. of the 88.5% solids solution. Proton NMR showed the 
polyester had a 71 fumarate to 29 maleate mol ratio of isomers. Molecular 
weight as determined by GPC was Mw=12,300, Mn=1250. 
EXAMPLE 16 
Preparation of Hydroxyl Terminated Polyester D 
A 1000 ml. four-necked flask equipped with a thermometer, nitrogen sparge 
tube, overhead stirrer and Barrett trap on top of a six inch steam 
jacketed Vigreux condenser was charged with 445.8 g. neopentyl glycol (4.3 
mols), 228.3 g. dimethyl cyclohexane-1,4-dicarboxylate, 1.6 g. dibutyltin 
oxide and 1.6 g. triphenyl phosphite. Steam was turned on in the jacketed 
Vigreux, and the mixture was stirred with a nitrogen sparge and heated to 
190.degree. C. After one hour, the temperature was increased to 
200.degree. C. and held there for a total of 4.5 hours during which time 
95% of the theoretical weight of distillate was collected. Actual weight 
loss, as determined by weighing the reaction mixture after allowing it to 
cool to room temperature, was 76.3 g. or 104.5% of the theoretical amount. 
There was then added 268.7 g. maleic anhydride (2.7 mols) and the mixture 
was reheated again under nitrogen but without steam in the jacketed 
Vigreux. Enough xylene was added through the condenser on top of the 
Barrett trap to cause steady reflux at a pot temperature of 200.degree. C. 
Refluxing was continued at that temperature for a total of 7 hours during 
which 58 ml. of aqueous distillate was collected and the acid titer of the 
mixture dropped to 0.022 meq per gram of reaction mixture. The product was 
then diluted to approximately 70% solids by adding xylene until the 
mixture refluxed at a pot temperature of 160.degree. C. Proton NMR of the 
polyester showed an isomer mol ratio of 58 fumarate to 42 maleate. 
Molecular weight as determined by GPC was Mw=7340, Mn=2330. 
EXAMPLE 17 
Preparation of Aminated Polyesters from Polyester D 
Polyester E. 
A 1000 ml. three-necked flask fitted with overhead stirrer and nitrogen 
sparge tube was charged with 480 g. of Polyester D which was stirred at 
room temperature in a nitrogen atmosphere while 17.3 g. 
3-(dimethylamino)propyl amine was added. A mildly exothermic reaction 
occurred and a pale yellow color developed. Proton NMR showed the product 
to have an isomer mol ratio of 87 fumarate to 13 maleate. 
Polyester F. 
A 500 ml. three-necked flask fitted with overhead stirrer and nitrogen 
sparge tube was charged with 240 g. of Polyester D which was stirred at 
room temperature in a nitrogen atmosphere while 7.9 g. of 
bis((3-dimethylamino)propyl amine) was added. A pale yellow color 
developed. Proton NMR showed the product to have an isomer mol ratio of 65 
fumarate to 35 maleate. 
Polyester G. 
A 300 ml. three-necked flask fitted with overhead stirrer and nitrogen 
sparge tube was charged with 102.3 g. of Polyester D. The polyester was 
stirred under nitrogen and heated to 100.degree. C. and 3.4 g. of 
bis((3-dimethylamino)-propyl amine was added. After a ten minute hold at 
100.degree. C. the mixture was allowed to cool to room temperature. This 
product was slightly darker in color than Polyesters E and F. Proton NMR 
showed an isomer mol ratio of 76 fumarate to 24 maleate. 
EXAMPLE 18 
Preparation of Trimethylolpropane Tris (acetoacetate) 
A 1000 ml. four-necked flask fitted with overhead stirrer, nitrogen sparge 
tube, thermometer and Barrett trap on top of a 6" steam jacketed Vigreux 
column was charged with 134.2 g. trimethylolpropane (1.0 mol), 580.6 g. 
methyl acetoacetate (5.0 mols), 0.8 g. triphenyl phosphite and 0.8 g. 
dibutyltin oxide. Steam was turned on in the jacketed Vigreux and the 
mixture was stirred with a nitrogen sparge and heated. When the pot 
temperature reached 142.degree. C. methanol began distilling rapidly from 
the mixture. Heating was continued for a total of 50 minutes to a maximum 
pot temperature of 185.degree. C. Vacuum was then applied and the excess 
methyl acetoacetate was removed first at 20 mm. Hg then at 1 mm. Hg with a 
maximum pot temperature of 180.degree. C. Yield of orange liquid product 
was 372.4 g., 96% of theory. A small amount of white solid formed in the 
sides of the flask after cooling to room temperature. This was removed by 
gravity filtration. Proton NMR showed 100% conversion based on integration 
of methylene adjacent to esterified oxygen relative to methyl of 
trimethylolpropane. 
EXAMPLE 19 
Preparation of Trimethylolpropane Tris(ethylmalonate) 
A 1000 ml. four-necked flask fitted with thermometer, nitrogen sparge tube 
and a 6" steam jacketed Vigreux with a Barrett trap on top was charged 
with 134.2 g. trimethylolpropane (1.0 mol), 800.0 g. diethyl malonate (5.0 
mols), 1.0 g. triphenyl phosphite and 1.0 g. dibutyltin oxide. Steam was 
turned on in the condenser and heating was begun with a nitrogen sparge. 
The mixture cleared but became cloudy again at approximately 130.degree. 
C. When the pot temperature reached 160.degree. C. ethanol began 
distilling from the mixture. Heating was continued for a total of 50 
minutes with a maximum pot temperature of 180.degree. C. Vacuum was then 
applied and excess diethyl malonate was removed. Temperature was allowed 
to fall rapidly to 100.degree. C. to avoid crossesterification reactions 
which could yield high molecular weight materials. Final stripping was at 
100.degree. C. with 1 mm. Hg. Yield of product was 412 g. (86% of theory). 
Proton NMR was consistent with the proposed structure. 
EXAMPLE 20 
Direct Comparison of Epoxy/Amine and Preformed Strong Base Activators Using 
the Same AAEM Copolymer with Both Activators, and Demonstration of 
Advantages in Water Resistance with TEDA when the Epoxy Component is an 
AAEM/GMA Copolymer Rather than a Low Molecular Weight Epoxide 
Blue paints were prepared as described above, using the following AAEM 
copolymers: 
AAEM Copolymer I: 40 AAEM/50 IBMA/10 DMAEMA 
AAEM Copolymer J: 40 AAEM/40 IBMA/20 GMA. 
The alkene component was Polyester H, a hydroxy terminated polyester 
prepared similarly to Polyester D. The mole ratio of reactants used to 
make the polyester was 20.4 neopentyl glycol/9.7 dimethyl 
cyclohexanedicarboxylate/9.7 maleic anhydride. The equivalent weight was 
435 grams/alkene group. Gel permeation chromatograph indicated Mw=7700, 
Mn=2770. 
The ratio of AAEM copolymer to polyester was 40/60, giving more economical 
but softer binders than illustrated in preceding examples. The comparison 
of preformed strong base and epoxy/amine activation was with AAEM 
copolymer I. The epoxy was a commercial example of bisphenol A diglycidyl 
ether (Epon 828, Shell). The latter epoxy/amine system was to be further 
compared with a system where the epoxy was from AAEM copolymer J, which 
was used at a 1/1 ratio with copolymer I (both then at 20 percent of total 
binder). 
The strong bases were tetrabutylammonium bicarbonate and 
tetramethylguanidine bicarbonate, both prepared by carbonation of 
methanolic solutions. The tetrabutylammonium bicarbonate solution 
introduced more methanol into the paint, so the tetramethylguanidine was 
evaluated both with the minimum methanol and also with additional methanol 
added to give the same level as with tetrabutylammonium. 
To test early cure and water resistance, pieces of the panels were exposed 
in a Cleveland Condensing (QCT) cabinet with the paint exposed to water 
vapor at 120 degrees F. and the backside of the panel exposed to ambient 
conditions. Table 8 gives hardness results. Table 9 gives gloss before and 
after exposure in the Cleveland Condensing cabinet, and rating of blisters 
developed during exposure. The exposure in the cabinet started after 1 day 
of ambient cure and lasted for 3 days. The level of methanol (MeOH) shown 
is weight percent of binder. 
TABLE 8 
__________________________________________________________________________ 
Hardness comparisons for Example 20. 
AAEM Additive Pencil 
Poly- 
MeOH Knoop Hardness 
1/4/7/14 
mer (Wt %) 
Epoxy 
Type Meq/100 g 
1/4/7 days 
days 
__________________________________________________________________________ 
J/I 0 GMA in I 
TEDA 28 0.5/1.3/1.9 
5B/B/B/HB 
J 1.7 None TMGCARB 
10 0.5/0.8/0.8 
3B/B/B/B 
J 2.6 None TMGCARB 
15 0.6/0.8/0.8 
3B/B/B/B 
J 0 6pctEpon 
TEDA 28 0.5/2.6/4.0 
3B/B/B/F 
J 10.0 
None TBACARB 
10 0.4/0.6/0.6 
5B/2B/B/B 
J 15.0 
None TBACARB 
15 0.5/0.6/0.7 
3B/B/B/B 
J 10.0 
None TMGCARB 
10 0.4/0.7/0.7 
3B/B/B/B 
J 15.0 
None TMGCARB 
15 0.6/0.8/0.8 
3B/B/B/B 
__________________________________________________________________________ 
TABLE 9 
__________________________________________________________________________ 
Condensing cabinet results for Example 20. 
AAEM Blisters 
Poly- Additive 20 Degree Gloss 
Size 
Density 
mer MeOH 
Epoxy 
Type Meq/100 g 
Before 
After 
(ASTM) 
__________________________________________________________________________ 
J/I 0 GMA in I 
TEDA 28 80.2 
75.8 
Micro 
MD 
J 1.7 None TMGCARB 
10 57.5 
9.6 7 D 
J 2.6 None TMGCARB 
15 53.7 
11.3 
3-5 D 
J 0 6pctEpon 
TEDA 28 81.3 
9.5 7 D 
J 10.0 
None TBACARB 
10 73.8 
68.0 
Micro 
D 
J 15.0 
None TBACARB 
15 65.9 
56.4 
Micro 
D 
J 10.0 
None TMGCARB 
10 70.7 
9.3 5-7 D 
J 15.0 
None TMGCARB 
15 66.8 
13.9 
3-5 D 
__________________________________________________________________________ 
MD = medium dense D = dense 
The hardness development was much better with amine/epoxy catalyst than 
with preformed strong base. The best gloss retention and blister 
resistance in the Cleveland Condensing Cabinet was with the system of the 
invention using GMA in an AAEM copolymer as epoxy. Methanol contributes to 
gloss with strong base activator, but gloss is still poor. 
Tetramethylguanidine gives very poor water resistance, with extremely 
severe blistering. Blistering is less severe, but still very bad when TEDA 
is used with low molecular weight epoxy resin. It is thought that blister 
resistance is related to low molecular weight water sensitive moieties 
that are osmotically active. High molecular weight water sensitive 
materials provide much less osmotic driving force for accumulation of 
water under the film. 
EXAMPLE 21 
Blue Paint Evaluation of Strong Base Activators for Blister Resistance with 
an AAEM Copolymer not Containing Amine to Show Blistering is a Problem in 
the Prior Art even without Amine 
Paints were prepared and tested as in the preceding example, except that 
the AAEM polymer composition was 40 AAEM/55 IBMA/5 Styrene. This was done 
to see if the strong base catalysts were more water resistant in a polymer 
without amine. Table 10 shows the results. 
TABLE 10 
__________________________________________________________________________ 
Evaluations of strong base catalysts with 40/60 AAEM 
copolymer/polyester binder using AAEM polymer composition 
40 AAEM/55 IBMA/5 Styrene. 
Knoop 
MeOH Hardness 
Pencil 
Gloss 
Blister 
Base (wt %) 
Meq/100 g 
1/7/14 day 
1/7/14 day 
In 
Out 
Size 
Density 
__________________________________________________________________________ 
TBACARB 10 10 0.5/0.9/1.8 
5B/B/B 
72 
61 Micro 
D 
TMGCARB 10 10 0.6/0.9/1.6 
2B/B/B 
68 
9 3-5 D 
TMGACETATE 
2.6 15 
/0.7/0.9 
/&lt;6B/6B Tacky at 1 day. 
DBUCARB 2.2 10 0.4/1.0/1.4 
4B/B/B 
73 
10 9 D 
DBUCARB 3.3 15 0.5/1.1/1.3 
3B/B/B 
67 
12 7-9 D 
DBUAcetate 
3.3 15 
/0.7/1.4 
/6B/5B Tacky at 1 day. 
__________________________________________________________________________ 
D = dense 
As shown by the gloss and blister results, the organic base activators TMG 
and DBU give poorer water resistance than tetrabutylammonium hydroxide, 
even with a polymer system that does not have amine, further 
distinguishing preferred epoxy/amine activator systems from activators 
taught by Brindkopke et. al. 
EXAMPLE 22 
Blue Paint Comparison of a Polyester Similar to that Used in Example 20 
with Amine Modified, Acrylate Modified, and Higher Fumarate Variants 
Polyester I was prepared by the same procedure and with the same raw 
materials as Polyester H of Example 20. The molecular weights indicated by 
GLC were Mw=9940, Mn=2820. Polyester J was prepared by addition, at room 
temperature, of DMAPA to Polyester I in the ratio of of 1 mole of DMAPA 
per 20.4 NPG. Polyester K was prepared by reaction of Polyester I with 2 
moles of the adduct between isophorone diisocyanate and hydroxyethyl 
acrylate per 20.4 NPG. The molecular weights were Mw=9310, Mn=1790. 
Polyester L was prepared similarly to Polyester I except that 4.85 moles of 
fumaric acid and 4.85 moles of maleic anhydride were used instead of 9.7 
moles maleic anhydride. The percent of the unsaturation present in the 
isomerized (fumarate) form in the final polyesters was 53 for Polyester I 
and 75 for Polyester L. GPC of polyester L indicated Mw=13,400, Mn=3720. 
Pigment dispersions prepared as described above were combined with 
additional AAEM copolymer, xylene, a silicone flow aid (SF-1023, General 
Electric), triethylenediamine as a solution in methyl ethyl ketone (MEK) 
and polyester to give paints with the following composition: 
______________________________________ 
Total AAEM copolymer solids 
4.0 grams 
Polyester solids 6.0 grams 
15 wt. percent DABCO in MEK 
0.8 grams 
SF-1023 0.01 grams 
Xylene 10.0 grams 
Phthalocyanine Blue 0.364 grams 
Titanium Dioxide 0.897 grams 
______________________________________ 
The paints were drawn with a block having a 7 mil gate on cold rolled steel 
panels (Phosphate pretreated using Bonderite 1000 (Parker) pretreatment). 
The compositions of the AAEM copolymers used were: 
Copolymer J: 40 AAEM/50 i-BMA/10 DMAEMA. (Mw/Mn=15,600/5900) 
Copolymer I: 40 AAEM/40 i-BMA/20 GMA. (Mw/Mn=14,600/7390) 
Copolymer K: 40 AAEM/50 n-BMA/10 GMA. (Mw/Mn=19,600/8880). 
In one set of comparison paints the AAEM copolymer solids were a 1/1 blend 
by weight of I and J. In another set of comparison paints the AAEM 
copolymer solids were all from K. Tables 11 and 12 show key results from 
evaluation of the films. 
TABLE 11 
______________________________________ 
Comparison of unmodified and amine or acrylate modified 
polyesters using AAEM Copolymers I and J. 
Polyester Identification 
I L K J 
______________________________________ 
Polyester Modification 
None None Acrylate 
Amine 
Fumarate/Maleate ratio 
53 75 about 53 
&gt;75 
47 25 about 47 
&lt;25 
Knoop Hardness at Days 
of Ambient Cure: 
1 day 0.4 0.5 0.6 0.4 
3 days 0.8 1.0 1.2 1.5 
7 days 1.3 1.5 2.0 2.3 
18 days 2.6 2.6 2.8 3.4 
Percent of original gloss 
88 88 94 93 
retained for 1 day ambient 
aged film exposed to high 
humidity in QCT chamber: 
Blistering in QCT chamber: 
9MD 9MD 9M 9MD 
______________________________________ 
TABLE 12 
______________________________________ 
Comparison of unmodified and amine or acrylate modified 
polyesters using AAEM Copolymers K. 
Polyester Identification 
I L K J 
______________________________________ 
Polyester Modification 
None None Acrylate 
Amine 
Fumarate/Maleate ratio 
53 75 about 53 
&gt;75 
47 25 about 47 
&lt;25 
Knoop Hardness at Days 
of Ambient Cure: 
1 day 0.4 0.5 0.5 0.5 
3 days 0.7 0.8 1.0 1.3 
7 days 1.0 1.0 1.4 1.8 
18 days 1.4 1.4 1.9 3.0 
Percent of original gloss 
62 76 91 92 
retained for 1 day ambient 
aged film exposed to high 
humidity in QCT chamber: 
Blistering in QCT chamber: 
9M 9M 9M 9D 
______________________________________ 
Note the superior cure of the amine-modified polyester indicated by 
improved hardness and the improved gloss retention of the acrylate and 
amine modified polyesters in the critical test for humidity resistance at 
one day of ambient cure. 
EXAMPLE 23 
Blue Paint Comparison of Polyesters Modified Using Increasing Levels of 
DMAPA, Study of Effect of Epoxy Level with Modified Polyesters 
A polyester (Polyester M) with the same composition as the Example 22 but 
with lower molecular weight (Mw=3730, Mn=1930) was reacted with DMAPA 
using 1, 2, 3, or 4 moles of DMAPA per 20.4 moles of NPG (polyesters N, O, 
P, and Q.) 
A pigment dispersion was prepared as described in Example 22, using an AAEM 
copolymer with composition 40 AAEM/55 IBMA/5 Styrene. This dispersion was 
used with the same AAEM copolymer to make paints with the following 
composition: 
______________________________________ 
Total AAEM copolymer solids 
3.4 grams 
Polyester solids 6.0 grams 
Epon 828 0.6 or 0.9 
grams 
SF-1023 0.01 grams 
Xylene 10.0 grams 
Phthalocyanine Blue 0.364 grams 
Titanium Dioxide 0.897 grams 
______________________________________ 
The paints were drawn with a block having a 7 mil gate on cold rolled steel 
panels (Phosphate pretreated using Bonderite 1000 (Parker) pretreatment). 
Tables 13 and 14 show key results from evaluation of the films. Note the 
improved cure as measured by hardness and resistance to humidity at one 
day going from one to two moles of DMAPA/average polyester molecule, and 
the loss in acid resistance going from two to three moles of DMAPA/average 
molecule. Note that with the higher levels of amine the cure improves with 
the higher level of epoxy resin. 
TABLE 13 
______________________________________ 
Comparison of polyesters using binder composition AAEM 
polymer/Epon 828/Polyester = 34/6/60. 
Polyester Identification 
N O P Q 
______________________________________ 
Moles DMPA/20.4 NPG 
1 2 3 4 
Knoop Hardness at Days 
of Ambient Cure: 
1 day 0.8 1.3 1.7 1.8 
3 days 1.4 2.7 4.7 3.0 
14 days 1.7 2.8 3.4 1.7 
Gloss after QCT exposure of 
37 71 62 49 
film exposed at 1 day ambient 
cure: 
Pencil hardness of wet 
6B 5B 5B &lt;6B 
film from QCT test: 
Pencil Hardness at Days 
of Ambient Cure: 
1 day 6B B HB HB 
3 days 2B B HB HB 
14 days B HB HB B 
Pencil hardness after 30 minute 
2B 5B &lt;6B &lt;6B 
patch test with 10% aqueous 
acetic acid (14 days cure): 
______________________________________ 
TABLE 14 
______________________________________ 
Comparison of polyesters using binder composition AAEM 
polymer/Epon 828/Polyester = 33/8.7/58.3. 
Polyester Identification 
O P Q 
______________________________________ 
Moles DMAPA/20.4 NPG 2 3 4 
Knoop Hardness at Days of 
Ambient Cure Shown: 
1 day 1.4 2.1 2.5 
3 days 2.6 7.3 8.5 
17 days 3.6 5.1 4.6 
Gloss after QCT exposure of 
73 36 52 
film exposed at 1 day ambient 
cure: 
Pencil hardness of wet film 
5B 5B 6B 
from QCT test: 
Pencil Hardness at Days 
of Ambient Cure: 
1 day B HB HB 
3 days B HB HB 
14 days HB HB HB 
Pencil hardness after 30 minute 
5B &lt;6B &lt;6B 
patch test with 10% aqueous 
acetic acid (14 days cure): 
______________________________________ 
EXAMPLE 24 
Accelerating Effect of Phenols and Alcohols 
Blue paints were prepared as described in Example 23, using the same AAEM 
copolymer and the 0.6 gram level of Epon 828 (binder composition AAEM 
copolymer/Epon 828/Polyester=34/6/60). The polyester was a repeat 
preparation of Polyester E (tertiary amine groups from bis-dimethylamino 
propylamine), with fumarate/maleate ratio by NMR=69/31 and molecular 
weights estimated by gel permeation chromatography of Mw=9370, Mn=2900. 
One paint was prepared without additional additives, the other paints with 
4 weight percent para-t-butyl phenol based on binder solids, with or 
without use of 2-ethylhexanol or capryl alcohol at 20 weight percent on 
binder solids and with or without 0.4 weight percent TEDA based on binder 
solids. 
Table 15 shows cure and viscosity progression for blue paints with or 
without p-t-butylphenol and the effect of using TEDA and/or octyl alcohols 
(2-ethylhexyl or capryl) with the phenol. 2-Ethylhexanol shortened the 
time to pass water spotting, but also shortened pot life and increased 
paint viscosity. It is clear that the phenol gave a dramatic improvement 
in time to pass water spot. With 4 wt. pct. phenol, 0.4 wt. pct. TEDA gave 
some further improvement in cure speed, while shortening pot-life but 
still allowing 6.5 hours to doubling of viscosity with this paint. A 
further benefit with 2-ethylhexanol seen here was improved resistance to 
blistering in high humidity. 
TABLE 15 
______________________________________ 
Effects of phenol, octyl alcohol and TEDA on cure of blue 
paints. 
Sample 1 2 3 4 5 6 
______________________________________ 
Alcohol None EthH Capr None None EthH 
Butylphenol 
None 4pct 4pct 4pct 4pct 4pct 
TEDA None None None None .4pct .4pct 
Early Cure 
Properties 
Viscosity 
10 minutes 
62 124 114 72 74 114 
150 minutes 
56 116 116 68 76 130 
330 minutes 
58 140 136 76 146 &gt;1000 
Tack Free (Hr) 
Zero Gram 
5-6 6-6.5 4-5.5 4-5.5 3-4 3-4 
500 Gram 8-9 7-7.5 8-9 6-7.5 6-7 6-7 
Water Spot 
Pass (Hr) 
12-19 4-5 5-7 5-7 4-5 3-4 
Film Properties 
(13 days 
ambient cure) 
Knoop 5.1 2.8 2.2 3.0 3.6 2.1 
Hardness 
Pencil HB B B HB HB B 
Hardness 
Blister after 
Mod. None Few Mod. Dense None 
4 Days High 
Micro Micro Micro Micro 
Humidity 
______________________________________ 
EXAMPLE 25 
Effect of Polyester Type on Cure and Water Resistance with Use of a Mixture 
of TEDA and Bis-DMAPA as Amines 
Pigment dispersions were prepared with titanium dioxide as sole pigment, 
using a sand grind procedure with AAEM copolymers as vehicle. The AAEM 
copolymers were prepared without mercaptan, using t-butyl peroctoate as 
initiator with 4.5 or 9.0 weight percent t-butyl peroctoate based on 
monomers. The monomer composition was 40 AAEM/52 i-BMA/8 GMA. AAEM 
copolymer L, prepared with 9.0 percent t-butyl peroctoate, had Mw=9,960, 
Mn=2760. AAEM copolymer M, prepared with 4.5 percent t-butyl peroctoate, 
had Mw=20,700, Mn=6910. 
Paints were prepared with 4.29 grams titanium dioxide and 10 grams of 
binder, with the binder solids being AAEM 
Polymer/Polyester/TEDA/bis-DMAPA/p-t-butyl phenol=56/40/0.5/1.5/2. The 
polyesters were: 
Polyester C Repeat (ethyl hexyl terminated, Mw/Mn=12,300/1250, 
Fumarate/Maleate=71/29). 
Polyester R: 8.7 NPG/2 ED204/9.7 MAnh, 9710/1800, 52/48, hydroxyl 
terminated. 
Polyester S: 6.7 NPG/1.42 ED204/7.12 MAnh, 6730/2290, 55/45, hydroxyl 
terminated. 
Polyester T: 4.44 NPG/1.11 ED204/4.55 MAnh, 4390/1760, 52/48, hydroxyl 
terminated. 
Polyester U: 4.44 NPG/1.11 ED204/6.55 DBM, 2500/1270, 23/77, butyl 
terminated. 
Polyester V: 4.44 NPG/1.11 ED204/6.55 DMM, 1810/1110, 12/88, methyl 
terminated. 
Polyester W: 4.44 NPG/1.11 ED204/4.55 MAnh//2.0 Acetic Anhydride, 
3560/1740, 46/54, acetate terminated. 
The paints were drawn with a 7 mil gate on phosphatized rolled steel 
(Bonderite 1000) and properties determined scribed in Tables 16 and 17. 
TABLE 16 
______________________________________ 
Viscosity progression, water spot test for early cure, and 
14 day ambient cure hardness as a function of AAEM polymer 
molecular weight and polyester type. 
AAEM VISC VISC KHN PNCL 
SAM- POLY- POLY- 12 8 WATER 14 14 
PLE MER ESTER MN HR SPOT DA DA 
______________________________________ 
1 L R 162 274 8 5.2 HB 
2 L C 106 356 &gt;9Sldull 
4.1 HB 
3 M C 156 266 &gt;9Sldull 
5.3 HB 
4 M S 190 414 7-8 5.5 HB 
5 M T 156 264 9+ 7.3 HB 
6 M U 106 166 &gt;9(Ring) 
2.7 B 
7 M V 102 154 &gt;9(Ring) 
2.6 B 
8 M W 128 200 &gt;9Sldull 
4.0 HB 
______________________________________ 
TABLE 17 
__________________________________________________________________________ 
Effect of AAEM polymer molecular weight and polyester type 
on humidity resistance. 
1 DAY AMBIENT CURE 
11 DAY AMBIENT CURE 
AAEM 20.degree. GLOSS 
BLISTER 
20.degree. GLOSS 
BLISTER 
SAMPLE 
POLYMER 
POLYESTER 
QCT 
3 DAY 
3 DAY 
QCT 
3 DAY 
3 DAY 
__________________________________________________________________________ 
1 L R 82.2 
74.0 
9MD 82.2 
60.0 
7-9D 
2 L C 81.0 
73.5 
MicFM 
82.3 
81.0 
9M 
3 M C 83.6 
77.5 
MicFM 
81.0 
82.0 
9FM 
4 M S 80.7 
67.0 
9D 83.0 
61.7 
5-7D 
5 M T 82.5 
65.0 
7-9D 83.1 
56.7 
5-7D 
6 M U 82.0 
76.0 
MicF 83.0 
81.4 
7-9MD 
7 M V 82.2 
73.7 
MicF 84.2 
79.1 
9D 
8 M W 82.9 
78.0 
MicFM 
83.0 
79.1 
7-9MD 
__________________________________________________________________________ 
QCT = 20 degree gloss when placed in Cleveland Condensing Cabinet witn 
water vapor at 120 degrees F., after one day ambient cure. 
3 DAY = 20 degree gloss or blister after 3 days exposure of ambient aged 
panels. 
Polyesters U and V, with low fumarate level, gave poorer cure as indicated 
by hardness at 14 days and poorer early cure as indicated by water spot 
test (ring at 9 hours) and some dulling when exposed to high humidity 
after 1 day ambient cure. 
However, the most dramatic response was the much poorer water resistance of 
the hydroxyl terminated polyesters R, S, and T indicated by blistering 
when exposed to high humidity after 1 or 11 days ambient cure. 
EXAMPLE 26 
Effect of Acceptor Type/Level on Hardness and Color 
This example demonstrates the superior color with TMPAOPATE as alkene 
component above a minimum level that is less than about 1 mole of 
alkene/mole of acetoacetate. 
White paints were prepared as described in Example 25, using AAEM Copolymer 
N and either TMPAOPATE or the repeat of Polyester C described in Example 
25. The binder composition for each paint contained a total of 9.15 grams 
AAEM copolymer plus alkene component (TMPAOPATE or Polyester C). The 
remainder was 0.6 grams Epon 828 and 0.25 grams bis-DMAPA. All paints also 
contained 0.2 grams p-t-butyl phenol and 0.01 grams Silicone SF-1023, with 
xylene as solvent. AAEM copolymer N was prepared with monomer composition 
40 AAEM/55 i-BMA/5 Styrene, 1 weight percent 
2,2'-azobis(2-methylbutanenitrile as initiator and 1% n-dodecyl mercaptan, 
and had Mw/Mn=21,900/9220. 
Paints were drawn with a 7 mil gate on phosphatized cold rolled steel 
(Bonderite 1000). At 1 day ambient cure pieces were placed in an oven at 
140 degrees F. for 24 hours, followed by measurement of hardness and 
yellowness. These properties were measured after 14 days cure at ambient. 
Results are shown in Table 18. 
TABLE 18 
__________________________________________________________________________ 
White paint study of acceptor type/level. 
DONOR/ 
ALKENE/ 
ACCEPT 
AAEM KHN DLTB 
KHN PNCL 
DLTB 
SAMPLE 
ACCEPTOR 
RATIO 
RATIO 
OVEN 
OVEN 
14 DA 
14 DA 
14 DA 
__________________________________________________________________________ 
1 None 91.5/0 
0.00 4.9 7.57 
1.3 5B 0.97 
2 TMPAOPATE 
85.5/6 
0.13 4.9 1.75 
1.3 3B 0.51 
3 TMPAOPATE 
79.5/12 
0.36 5.4 0.16 
2.1 B 0.09 
4 TMPAOPATE 
73.5/18 
0.63 6.8 -0.33 
3.8 B -0.18 
5 TMPAOPATE 
67.5/24 
0.96 6.8 -0.13 
6.6 F -0.07 
6 TMPAOPATE 
61.5/30 
1.33 7.6 -0.20 
8.8 F -0.12 
7 Polyester C 
54/37.5 
1.59 8.7 5.92 
6.5 F 2.22 
__________________________________________________________________________ 
EXAMPLE 27 
Effect of Alkene/Acetoacetate on Color with Trimethylolpropane Triacrylate 
as Alkene Component 
This example shows that good color was obtained when the 
alkene/acetoacetate ratio was above about 2 and that good hardness was 
retained at an alkene/acetoacetate ratio of 3 with trimethylolpropane 
triacrylate as the alkene component. 
White paints were prepared and tested as in Example 26, with AAEM Copolymer 
N and various levels of TMPTA as alkene component and a total of 9.4 grams 
AAEM copolymer plus TMPTA, with 0.6 grams Epon 828, 0.25 grams bis-DMAPA, 
and 0.2 grams p-t-butyl phenol. 
Results are shown in Table 19. The abbreviations are the same as for Table 
18. 
TABLE 19 
__________________________________________________________________________ 
White paint study of various levels of TMPTA as alkene component. 
ALKENE/ 
AAEM KHN DLTB 
KHN PNCL 
DLTB 
SAMPLE 
ACCEPTOR 
BINDER 
RATIO 
OVEN 
OVEN 
14 DA 
14 DA 
14 DA 
__________________________________________________________________________ 
1 TMPTA 75/19/6 
1.15 13.0 
3.34 
15.3 
2H 0.18 
2 TMPTA 70/24/6 
1.63 16.9 
1.05 
18.8 
2H -0.09 
3 TMPTA 65/29/6 
2.19 15.0 
0.41 
15.0 
2H -0.29 
4 TMPTA 60/34/6 
2.84 13.8 
-0.41 
14.8 
2H -0.21 
5 TMPTA 55/39/6 
3.60 11.8 
0.18 
12.0 
2H -0.32 
__________________________________________________________________________ 
EXAMPLE 28 
Demonstration of Superior Color with Malonate as Donor 
A malonate functional acrylic copolymer was prepared by treatment of a 
hydroxyl functional acrylic with an excess of diethyl malonate in the 
presence of 0.5 wt % dibutyl tin oxide, removing ethanol formed by 
transesterification at a temperature of 180 degrees C. The hydroxyl 
function acrylic had composition 61.5 iBMA/26.2 HEMA/12.3 MMA, 
Mw/Mn=27,100/9630. The product was diluted with xylene, giving a solution 
having 65.8 weight percent of polymer with pendant malonate groups, about 
218 grams polymer per active methylene group, in 75/25 xylene/diethyl 
malonate. The molecular weight as estimated by gel permeation 
chromatography was Mw/Mn=47,700/11,900. 
AAEM copolymers 0 and P were prepared with 4.5 weight % t-butyl peroctoate. 
Copolymer 0 had monomer composition 40 AAEM/50 iBMA/10 MMA, 
Mw/Mn=16,500/6180. AAEM copolymer P had monomer composition 30 AAEM/50 
iBMA/20 MMA, Mw/Mn=16,000/6080. 
Clear enamels were prepared at 60 weight percent solids in xylene, with 
acrylic polymer plus alkene component=9.15 grams, 0.6 grams Epon 828, 0.25 
grams bis-DMAPA, and 0.2 grams t-butyl phenol comprising the solids. 
Alkene components used were Polyester R and TMPTA. 
The enamels were drawn with a 7 mil gate on phosphatized cold rolled steel 
(Bonderite 1000) and two glass plates. One of the glass plates was held in 
an oven at 140 degrees F. for 24 hours after 1 day ambient cure. The other 
glass plate was kept at ambient with the steel panel. Table 20 shows the 
yellowness index for the heated plate and hardness and yellowness index at 
14 days for the panel and ambient plate. 
With the heat-aged panels there was much less yellowness with the malonate 
polymer as acceptor over the range of binder compositions tested. 
TABLE 20 
__________________________________________________________________________ 
Clear film comparison of AAEM polymers and Malonate polymer 
with polyester R and TMPTA as acceptors. 
CO- POLY- DONOR 
MOL KCLR 
KHN PNCL 
KCLR 
SAMPLE 
POLYMER 
ESTER 
BINDER 
EQ RATIO 
OVEN 
14 DA 
14 DA 
14 DA 
__________________________________________________________________________ 
1 AAZM O 
R 61.5/30/6/2.5 
111 1.0 10.76 
5.8 F 2.35 
2 AZAM P 
R 61.5/30/6/2.5 
83 1.4 8.95 
4.0 HB 2.15 
3 Malonate 
R 61.5/30/6/2.5 
101 1.1 5.56 
5.1 F 2.30 
4 AAEM O 
TMPTA 
76.5/15/6/2.5 
138 0.9 7.13 
9.2 F 1.61 
5 AAEM P 
TMPTA 
76.5/15/6/2.5 
103 1.2 5.61 
10.1 
F 1.18 
6 Malonate 
TMPTA 
76.5/15/6/2.5 
125 1.0 1.34 
10.2 
F 1.15 
7 AAEM O 
TMPTA 
71.5/20/6/2.5 
129 1.4 4.86 
11.4 
H 1.39 
8 AAEM P 
TMPTA 
71.5/20/6/2.5 
96 1.8 1.22 
11.1 
H 1.78 
9 Malonate 
TMPTA 
71.5/20/6/2.5 
117 1.5 0.72 
10.5 
H 1.15 
__________________________________________________________________________ 
EXAMPLE 29 
Demonstration of Cure with Acetoacetate and Malonate Reactive Diluents and 
Color Advantage with Malonate Reactive Diluent Relative to Acetoacetate 
Preparation of tris-malonate and tris-acetoacetate reactive diluents is 
described in Examples 18 and 19. The AAEM polymer used was prepared with 
monomer composition 40 AAEM/55 iBMA/5 Styrene, using 2.3 weight percent 
based on monomers of 2,2'-azobis(2-methylbutanenitrile) as initiator. The 
molecular weights estimated by gel permeation chromatography were 
Mw/Mn=20,000/9120. 
White paints with 4.29 grams titanium dioxide and 10 grams binder solids 
were tested with variation of weight ratio of AAEM polymer to polyester 
and with use of a combination of reactive diluent and AAEM polymer. The 
total weight of AAEM polymer plus reactive diluent plus polyester was 9.4 
grams, with 0.6 Epon 828. The polyester was prepared from 20.4 NPG/9.7 
DMCD/9.7 MAnh, aminated with 2.0 dimethylaminopropylamine. The 
fumarate/maleate ratio estimated by NMR was 85/15 and the molecular 
weights estimated by gel permeation chromatography were Mw/Mn=3730/1930. 
Films were drawn with a 7 mil gate on phosphatized cold rolled steel 
(Bonderite 1000). Results are shown in Table 21. 
TABLE 21 
__________________________________________________________________________ 
Comparison of tris-malonate and tris-acetoacetate diluents. 
REACTIVE WTPC 
VISC KHN PNCL REV KCLR 
DILUENT 
WT RATIO 
SOLD 
4 MIN 
14 DA 
14 DA 
IMT 
14 DA 
__________________________________________________________________________ 
None 34/0/60 
57.2 
40 5.2 HB 30-50 
9.7 
None 40/0/54 
57.2 
40 5.9 HB 30-50 
9.9 
None 46/0/48 
57.2 
56 4.9 HB 10-20 
10.6 
TMPMal 
10/17/67 
65.2 
70 4.5 HB &gt;110 9.7 
TMPAcAc 
10/17/67 
65.2 
70 1.9 B 20-30 
12.6 
__________________________________________________________________________ 
The hardness with the malonate reactive diluent approached that of the 
binders without reactive diluent, while the color was as good and the 
viscosity/solids was much better. The acetoacetate reactive diluent gave 
poorer color and hardness. 
EXAMPLE 30 
Demonstration of Superior Chemical Resistance Properties with Use of 
Isocyanate and Hydroxyl Functional Polyesters 
Clear enamels were prepared with an AAEM copolymer prepared using monomer 
composition 40 AAEM/55 iBMA/5 Styrene and 2.3 wt. percent 
2,2'-azobis(2-methylbutanenitrile) as initiator, giving molecular weights 
Mw/Mn=19,400/8450. The polyester was prepared from 9.7 NPG/1 ED204/2.85 
DMCD/6.85 MAnh, aminated with 0.5 bis-DMAPA, giving a fumarate/maleate 
ratio of 74/26 and Mw/Mn=5710/2230. 
The isocyanate components were Isocyanate A, an m-tetramethylxylene 
diisocyanate/trimethylolpropane adduct with 8.6% isocyanate at 80% solids 
from American Cyanamid, and Isocyanate B, an isophorone diisocyanate 
trimer with 12.4% isocyanate at 70% solids from Chemische-Werke Huls. 
The other binder component was Epon 828. Enamels were prepared at 50 weight 
percent solids with xylene as solvent. Comparison was made between a 
binder having no isocyanate and no preformed strong base (sample 3), the 
same binder but with 10 milliequivalents/100 grams binder strong base in 
the form of tetramethylguanidine carbonate (sample 4), and binders with 
replacement of part of the AAEM copolymer and polyester with isocyanate A 
or B (samples 1 and 2). The binders with isocyanate have about 1 
isocyanate per hydroxyl end group of the polyester. 
Films were drawn with a 7 mil gate on phosphatized cold rolled steel and 
glass (for measurement of swell ratio) and properties measured as shown in 
Table 22. 
TABLE 22 
__________________________________________________________________________ 
Clear film evaluation of dual isocyanate/C-Michael cure. 
ISO TMG- 
VISC 
VISC VISC WATER 
KHN KHN PNCL 
SAMPLE 
CYAN 
BINDER 
CARB 
2 MIN 
TIM 2 TIM 3 
SPOT 1 DA 
7 DA 
7 DA 
__________________________________________________________________________ 
1 A 28/5/50/17 
0 92 140/2 hr 
260/3 hr 
6-7 1.7 9.6 H 
2 B 30/5/53/12 
0 64 254/98 m 
640/3 hr 
6-7 0.8 6.2 F 
3 None 
34/6/60/0 
0 66 70/90 mn 
76/3 hr 
&gt;9 0.5 4.4 HB 
4 None 
34/6/60/0 
10 70 Glng 57 mn 
Gel/75 mn 
&lt;3.5 0.6 4.1 B 
__________________________________________________________________________ 
SWRAT KHN PNCL HOAC HOAC HOAC NAOH NAOH 
SAMPLE 
7 DA 14 DA 
14 DA 
30 MN 
3.5 H 
6.5 H 3.5 H 6.5 H 
__________________________________________________________________________ 
1 1.59 16.3 H HB B 6B/SlMWh 
F HB 
2 1.61 8.4 F F HB B F F 
3 1.61 6.8 F B 3B &lt;6B B/SlMWh 
B/ModWh 
4 1.47 4.3 HB 2B &lt;6B &lt;6BBlstr 
B/SlMWh 
B/SlMWh 
__________________________________________________________________________ 
ISO CYAN: Isocyanate. 
BINDER: Weight ratio (solids) of AAEM copolymer/Epon 
828/Polyester/Isocyanate. 
TMG-CARB: Meq. preformed strong base/100 grams binder. 
VISC 2MIN: viscosity at 2 minutes after mixing (cps.). 
VISC TIM 2: Viscosity/time (cps/minutes (mn) or hours(hr)). 
VISC TIM 3: Viscosity/time (cps/minutes (mn) or hours(hr)). 
WATER SPOT: Hours to absence of effect from drop of water allowed to dry on 
film. 
KHN 1 DA: Knoop hardness at 1 day ambient cure. 
KHN 7 DA: Knoop hardness at 7 days ambient cure. 
PNCL 7 DA: Pencil hardness at 7 days ambient cure. 
SWRAT 7 DA: Volumetric swell ratio in butyl acetate at 7 days ambient cure. 
KHN 14 DA: Knoop hardness at 14 days ambient cure. 
PNCL 14 DA: Pencil hardness at 14 days ambient cure. 
HOAC 30 MN: Pencil hardness at 14 days after 30 minutes exposure to 10% 
acetic acid in water. 
HOAC 3.5 H: Pencil hardness after 3.5 hours exposure to 10% acetic acid in 
water. 
HOAC 6.5 H: Pencil hardness after 6.5 hours exposure to 10% acetic acid in 
water. 
NAOH 3.5 H: Pencil hardness after 3.5 hours exposure to 10% sodium 
hydroxide in water. 
NAOH 6.5 H: Pencil hardness after 6.5 hours exposure to 10% sodium 
hydroxide in water. 
Glng: Gelling. 
Gel: Gelled. 
SlMWh: Slight to moderate whitening. 
ModWh: Moderate whitening. 
The samples with the isocyanates have superior resistance to aqueous acetic 
acid and aqueous sodium hydroxide.