A class of new oxygen-activated free-radical polymerization catalysts, comprising specifically-defined autoxidizable cyclic hydrocarbons together with cobalt(II) compounds, is disclosed. A method of catalyzing an oxygen-initiated free-radical polymerization reaction using these catalysts is also disclosed.

TECHNICAL FIELD 
The present invention relates to new oxygen-activated free-radical 
polymerization catalysts and a method for catalyzing a free-radical 
polymerization reaction using these materials. 
BACKGROUND OF THE INVENTION 
Objects tend to be particularly vulnerable at their surfaces. The surfaces 
of objects left in the open bear the brunt of the sun, rain, fog, dew, ice 
and snow. Under these conditions iron rusts, wood rots and road surfaces 
crack and disintegrate, just to name a few of the possible consequences. 
Even sheltered objects, such as those found in the home, suffer the wear 
of daily use: scratches, dents and abrasions, at their surfaces. To 
prevent or to minimize such damage, coatings designed to protect surfaces 
are frequently applied. Coatings can also be used to decorate articles: to 
add color, luster, or to smooth out roughness or irregularities caused in 
the manufacturing process. Thus, in selecting a surface coating for a 
particular object there is a constant balancing which must go on between 
providing the necessary and appropriate protection and decoration 
functions. A wide variety of surface coatings is available, e.g., 
wallpaper, plastic sheets, chrome and silver plating. However, one of the 
most economical and versatile coatings is paint, which can be applied to 
any surface, however awkward its size or shape, by one process or another. 
Most paints contain liquid resinous or polymeric materials, known as 
binders. It is this component which, after conversion to a solid through 
the paint's drying process, provides a surface film having the necessary 
attributes of adhesion, flexibility, toughness and durability. Paints can 
generally be subdivided into two broad categories: convertible and 
non-convertible coatings. A convertible coating is a paint in which the 
binder is either a polymer precursor, a monomer or a partially polymerized 
material. Upon addition of a suitable initiator or exposure to radiant 
energy, such as ultraviolet or infrared radiation, the monomeric or 
partially polymerized component of the paint undergoes a polymerization 
reaction in which the binder is converted from a liquid or a soluble state 
into an insoluble solid material film. Nonconvertible coatings, in 
contrast, do not undergo curing or chemical conversion reactions when they 
dry. For these paints, film formation involves loss or evaporation of a 
volatile solvent or dispersion medium and the concomitant deposition of 
the solid binder material; it is critical that this deposition be both 
uniform and continuous. See Boxall, et al., Concise Paint Technology, 
Chemical Publishing, New York, 1977, especially pages 29-57; and Turner, 
Introduction to Paint Chemistry, Chapman and Hall Ltd, 1967, especially 
pages 95-107. 
BACKGROUND ART 
Polymerization reactions involving simple monomers, i.e., vinyl cyclic 
acetals, in the presence of oxygen and cobalt salts, to produce polymeric 
materials are well-known in the art. See, for example, Hochberg, J. Oil 
and Colour Chemists Assoc., 48, 1043-1068 (1965) and U.S. Pat. No. 
3,190,878, issued June 27, 1965, British Specification No. 916,563, 
published Jan. 23, 1963, and German Specification No. 1,148,033, published 
May 2, 1963, all assigned to E. I. duPont de Nemours & Co. The reaction of 
itaconic acid with vinyl acetate to form polyvinyl itaconate is also 
known. Akashi, Kogyo Kagaku Zasshi, 66, 156 (1963). Polymerization 
reactions of acrylic-terminated oligomers, initiated through the use of 
ultraviolet light, have been disclosed. Prane, Polymer News, 4, 239-241 
(1978). The use of benzaldehyde, in the absence of oxygen, as an initiator 
for the free radical polymerization of methyl methacrylate has been 
disclosed. Imoto, et al., J. Poly. Sci., 17, 385-392 (1979). 
U.S. Pat. No. 4,244,850, Mylonakis, issued Jan. 13, 1981, describes a paint 
composition containing preformed aqueous emulsion acrylate copolymer 
particles to which have been attached ethylenically unsaturated side 
chains. The acrylate copolymer, formed by emulsion polymerization, is made 
from butyl acrylate, methyl methacrylate and methacrylic acid. The 
unsaturated side chain is attached to the preformed particles in the 
emulsion via a post reaction of the free carboxylic acid groups with 
glycidyl methacrylate. 
In formulating a paint, especially an interior wall paint, the key 
characteristics to be kept in mind, in addition to aesthetics, are 
convenience of use, durability and ease with which the painted surface may 
be cared for. Further, when formulating a solvent-based paint, it is 
desirable to have a high solids content. Paints with low solids content 
have increased amounts of solvent; this is generally considered 
undesirable by consumers since ultimately the solvent just evaporates off. 
The paint should have excellent hiding properties (one-coat hiding is 
best); it should form a film which is stain resistant and easy to clean; 
it should have a high degree of surface continuity; and, finally, it 
should be durable, strong and resistant to wear. 
SUMMARY OF THE INVENTION 
The present invention relates to a new class of oxygen-activated 
free-radical polymerization catalysts which consist essentially of 
mixtures of peroxide-decomposing transition metal catalysts, such as a 
cobalt(II) compound, together with hydrocarbon compounds selected from the 
group consisting of 
##STR1## 
and mixtures thereof, wherein each R.sub.3 is hydrogen, methyl, phenyl or 
COOH; R.sub.4 is C.sub.1 -C.sub.20 alkyl or alkenyl; and n is from 1 to 
10. These catalysts are especially useful in the paint and plastic 
compositions claimed in concurrently-filed U.S. patent application Ser. 
No. 290,918, Bush and Robbins, "Agents for Preparing Cross-Linked Polymers 
and Paint and Plastic Compositions Containing These Agents", incorporated 
herein by reference. 
The catalysts are used in oxygen-initiated free-radical polymerization 
reactions whereby a resin material, capable of free-radical 
polymerization, is exposed to oxygen in their presence. 
DETAILED DESCRIPTION OF THE INVENTION 
Polymer Precursor Materials 
The essence of the present invention resides in a class of agents for 
preparing cross-linked polymers; these agents, when reacted under 
appropriate conditions, undergo a cross-linking polymerization reaction 
forming a strong, durable polymeric film which is the basis of the paint 
and plastic compositions defined herein. 
These agents are made up of two components: a major proportion of a low 
molecular weight backbone, and a minor proportion of mono- or 
disubstituted olefinic groups pendant from that backbone. It is preferred 
that the ratio, by weight, of pendant groups to backbone is from about 
0.05:1 to about 1:1, most preferably from about 0.1:1 to about 0.5:1. The 
backbone segment of the agent is selected from the group consisting of 
polyacrylates, polymethacrylates, polyesters, polyurethanes, 
polycarbonates, polyepoxides, polyvinyls, polystyrenes, or mixtures 
thereof, having a molecular weight of from about 1,000 to about 10,000; 
the preferred backbones for agents of the present invention being 
polycarbonates and, especially, polyacrylates. The precise backbone 
structure to be used in a particular application is chosen based on the 
mechanical strength, environmental resistance, and facility to perform 
post-oligomer chemistry (i.e., the ability to attach functional groups) 
required. 
Examples of such backbone materials and procedures for synthesizing them 
are disclosed in Boxall, et al., Concise Paint Technology, Chemical 
Publishing Co., Inc. New York, 1977, pages 29-57, incorporated herein by 
reference. Thus, for example, acrylic resins are polyvinylidene compounds 
having the general formula 
##STR2## 
wherein X commonly may be H, CH.sub.3, C.sub.2 H.sub.5, and Y is usually 
COOH or COOCH.sub.3. Epoxy resins are cross-linked polymers derived from 
reactions involving the epoxide or oxirane grouping 
##STR3## 
Epoxy resins may be produced by the reaction of bisphenol and 
epichlorhydrin. Polyurethane resins are polymers containing the urethane 
group, 
##STR4## 
within the main polymer backbone; they are formed by the reaction of 
isocyanates, R--NCO, with hydroxyl compounds. Preferred polycarbonates 
have the structure: 
##STR5## 
The pendant groups are mono- or di-substituted olefinic groups, with the 
olefinic substituents being unpolymerized. To be useful in the present 
invention, the pendant groups should be susceptible to free radical 
polymerization and polymerize at an acceptable rate, upon appropriate 
initiation, at room temperature in an oxygen atmosphere. Preferred pendant 
groups have a polymerization rate constant (measured at 70.degree. C.) 
between about 10.times.10.sup.-4 and about 1000.times.10.sup.-4, 
especially between about 10.times.10.sup.-4 and about 600.times.10.sup.-4, 
more preferably from about 60.times.10.sup.-4 to about 
600.times.10.sup.-4, moles.sup.-1/2 liter.sup.1/2 minute.sup.-1. 
Particularly preferred pendant groups are those selected from the group 
consisting of mono-methyl itaconate, 4-allyl-2-methylenesuccinate 
(beta-allyl itaconate), 1-vinyl-2-methylenesuccinate (alpha-vinyl 
itaconate), p-vinylbenzoic acid, monovinyl maleate, methyl methacrylate, 
4-vinyl-2-methylenesuccinate (beta-vinyl itaconate), 
N-phenyl-2-methylenesuccinimide, substituted 
N-phenyl-2-methylenesuccinimides and mixtures thereof; vinyl and allyl 
itaconates, especially alpha-vinyl, beta-vinyl and beta-allyl itaconates, 
are particularly preferred pendant groups. 
The polymerization rate constant (K') of a specific monomer or, as used 
herein, pendant group is equal to the rate of disappearance of the 
particular monomer (rate) divided by the product of the initial 
concentration of that monomer in solution (M) and the square root of the 
concentration of azobisisobutylnitrile (AIBN) in the system being tested. 
##EQU1## 
The rate is determined by heating a solution of monomer (pendant group) and 
AIBN at 70.degree. C. and determining the change in concentration of 
monomer with time (mole/liter minute), using chlorobenzene as the solvent 
under an argon atmosphere. K' is usually determined with monomer 
concentrations in the range of from about 0.02 L to about 2 mole/liter, 
while the concentration of AIBN is about 10 mole percent of the monomer 
concentration. For example, the polymerization rate constant for dimethyl 
itaconate was determined in the following manner. A chlorobenzene solution 
containing 2.23 mole/liter dimethyl itaconate, 0.23 mole/liter 
azobisisobutylnitrile, and 2.0 mole/liter dimethyl adipate (internal 
standard for gas chromatographic analysis) was subjected to three 
freeze-pump-thaw cycles, using liquid nitrogen to cool the sample and 
argon as the inert gas. After all the air had been replaced with argon, 
the reaction solution was placed in a bath at 70.0.degree. C. and the 
disappearance of dimethyl itaconate was followed by gas chromatography 
until 20% of the dimethyl itaconate had polymerized. A plot of time vs. 
concentration of dimethyl itaconate yielded the rate data: rate (in 
mole/liter minute) is the slope of the plot. K' can then be calculated 
using equation (1). 
The following table illustrates the polymerization rate constants of a 
range of pendant groups; some falling inside and some falling outside the 
scope of the present invention. 
______________________________________ 
POLYMERIZATION RATE CONSTANTS OF 
PENDANT GROUPS (AT 70.degree. C.) 
(.times. 10.sup.4 mole.sup. -1/2 liter.sup. 1/2 minute.sup. 
______________________________________ 
-1) 
Alpha-allyl itaconate 24 
vinyl succinate 26 
beta-allyl itaconate 34 
allyl maleate 35 
dimethyl itaconate 38 
vinyl octanoate 54 
mono-methyl itaconate 107 
alpha-vinyl itaconate 111 
p-vinylbenzoic acid 113 
vinyl maleate 114 
methyl methacrylate 173 
phenyl alpha-methylenesuccinimide 
495 
beta-vinyl itaconate 563 
vinyl chloride 8,480 
vinyl acetate 8,608 
methyl acrylate 18,944 
______________________________________ 
Materials with polymerization rate constants below the defined range 
polymerize too slowly to be practical for use in paint or plastic 
compositions, while the materials with higher polymerization rate 
constants (e.g., methyl acrylate, vinyl chloride, and vinyl acetate) 
polymerize in a rapid and uncontrolled manner, making their use 
unfeasible. 
Preferred agents of the present invention (i.e., those having a 
polyacrylate backbone and vinyl itaconate or allyl itaconate pendant 
groups) have the formulae 
##STR6## 
wherein R.sub.1 is hydrogen or methyl; R.sub.2 is hydrogen or an alkyl 
substituent; R.sub.3 is vinyl or allyl; a is from about 10 to about 100; b 
is from about 0.1a to about a; and c is from about 1 to about 20. Most 
preferred agents are those having the formulae 
##STR7## 
wherein R.sub.2 is C.sub.1 -C.sub.5 alkyl; R.sub.3 is vinyl or allyl; a is 
from about 10 to about 100, preferably from about 16 to about 48; b is 
from about 0.1a to about a, preferably from about 6 to about 12; c is from 
about 1 to about 5; and d is from about 0.3b to about 0.5b, preferably 
from about 2 to about 6. Preferred beta-vinyl itaconate pendant groups are 
described in concurrently-filed U.S. patent application Ser. No. 290,907, 
Bush, "4-vinyl-2-methylene-butanedioic Acid Compounds", incorporated 
herein by reference. 
The agents of the present invention may be prepared, using conventional 
methods, for example, in the following manner: 
A reaction flask is continually flushed with inert gas (e.g., argon) and 
charged with the following ingredients: the backbone resin, the acid 
chloride of the olefinic pendant group, and ethyl acetate. To this 
solution is added dropwise, with vigorous stirring, an ethyl acetate 
solution of an organic base capable of taking up the liberated HCl and 
also of catalyzing the reaction. Insoluble inorganic bases, such as 
calcium carbonate or ion exchange resins, can be used instead of the 
organic base, but they additionally require a base catalyst, such as 
pyridine or triethylamine. Where an inorganic base is used, the olefinic 
pendant group is added dropwise to a well-stirred dispersion of the 
insoluble base, the backbone resin and the base catalyst in ethyl acetate. 
After the base addition is complete, the reaction is worked up immediately 
in the following manner: the reaction mixture is filtered to remove 
precipitated amine hydrochloride, washed with saturated sodium bicarbonate 
to remove any unreacted acid chloride pendant groups or free HCl, and 
concentrated to remove the ethyl acetate solvent. 
Catalysts 
The polymer precursor materials of the present invention are usefully 
combined with catalyst materials (i.e., latent radical initiators) which, 
when initiated in an appropriate manner, as by introduction of oxygen, 
ultraviolet radiation, heat or light into the system, cause the precursor 
materials to undergo free radical polymerization forming a cross-linked 
polymer film. Although any type of catalyst effective in a free radical 
polymerization reaction may be used, when formulating paint compositions, 
it is especially preferred to combine the polymer precursor materials of 
the present invention with a catalytic amount of an oxidative catalyst 
sufficient to cross-link from about 2% to about 60%, preferably at least 
about 10%, most preferably at least about 20% of the pendant groups of the 
precursor within about 48 hours upon exposure to air at a temperature of 
about 20.degree. C. Compositions comprising the precursor materials and 
such oxidative catalysts generally contain from about 0.5% to about 5%, by 
weight, of the catalyst. 
An especially preferred catalyst for use in the present invention is a 
two-component system consisting of: (a) a specifically-defined hydrocarbon 
component and (b) a peroxide-decomposing transition metal catalyst. In 
order for a hydrocarbon to function effectively in such catalyst systems, 
it first has to be capable of autoxidation to form a hydroperoxide. In a 
hydrocarbon R.sub.1 R.sub.2 R.sub.3 CH, the selection of substituents 
R.sub.1, R.sub.2 and R.sub.3 so as to lower the dissociation energy of the 
carbon-hydrogen bond will be essential to performance in the catalyst 
system; thus hydrocarbons which readily autoxidize are most useful in the 
catalysts of the present invention. However, it is not only sufficient to 
have a hydrocarbon which autoxidizes rapidly, but it is also essential 
that the intermediate hydroperoxide formed decompose homolytically at a 
rate faster than it is being formed. The hydrocarbon component is most 
preferably selected from the group consisting of 
##STR8## 
and mixtures thereof, wherein each R.sub.3 is hydrogen, methyl, phenyl or 
COOH; R.sub.4 is C.sub.1 -C.sub.20 alkyl or alkenyl; and n is from 1 to 
10. The aromatic groups may be substituted; however, replacement of the 
oxygens with nitrogen atoms will significantly reduce the efficacy of 
these catalyst systems. Preferred hydrocarbon components are those having 
the formulae: 
##STR9## 
and mixtures thereof. A preferred class of hydrocarbon components is the 
2-alkyl substituted 1,3-dioxolanes, with 1,3-bis(1,3-dioxolan-2-yl)propane 
being especially preferred. 
The peroxide-decomposing transition metal catalyst component is preferably 
a cobalt(II) compound. Such compounds are well-known in the art and most 
frequently are cobalt(II) salts of carboxylic acids or a 2,4-pentanedione 
complex of cobalt(II). Examples of such compounds include cobalt(II) 
dipivalolylmethane, cobalt(II) acetylacetonate, cobalt(II) acetate, 
cobalt(II) decanoate, coablt(II) naphthenate, and mixtures thereof. In 
forming these preferred catalysts for use in the present invention the 
mole ratio of hydrocarbon component to transition metal catalyst 
(cobalt(II) compound) is from about 5 to about 5,000, most preferably from 
about 10 to about 1,000. 
Although the catalysts, defined above, are particularly useful in 
combination with the precursor materials of the present application, they 
have a more general use in catalyzing oxygen-initiated free radical 
polymerization reactions using any suitable precursor materials. In fact, 
these catalysts provide a generalized method for catalyzing 
oxygen-initiated free radical polymerization reactions wherein a resin 
material capable of free radical polymerization is exposed to oxygen in 
the presence of an effective amount of the catalyst consisting essentially 
of: (a) hydrocarbon catalyst compound, as defined above, and (b) a 
peroxide-decomposing transition metal compound, as defined above, 
especially a cobalt(II) compound. In such a polymerization reaction the 
ratio, by weight, of resin to catalyst (i.e., the combination of 
hydrocarbon and transition metal compound) is from about 5:1 to about 
200:1. As used above, the phrase "effective amount" indicates an amount of 
catalyst material used to effectively catalyze the cross-linking 
polymerization reaction. For any given reaction, the precise amount of 
catalyst required will be dependent upon the reaction conditions, the 
particular resins to be used, and the speed and completeness of the 
reaction desired; this amount for any given set of reaction materials and 
conditions is easily determined by one skilled in the art. 
The catalyst system, as defined above, may additionally contain a storage 
stabilizer component. Storage stabilizers (i.e., a polymerization 
inhibitor) act to assure that the free radical polymerization will not 
occur until the resin and catalyst mixtures have been exposed to oxygen or 
another appropriate initiator; however, they should not interfere with the 
operation of the catalyst system when polymerization is desired. Such 
storage stabilizers generally act by scavenging and tying up any itinerant 
free radicals which may be present in the system. Thus, for example, in 
formulating a paint composition of the present invention, the resin, the 
catalyst and a storage stabilizer are all included in the containers of 
paint; this assures that the polymerization will not take place until the 
paint is applied to a surface and exposed to oxygen. A particularly useful 
storage stabilizer is tetraphenylverdazyl, having the formula 
##STR10## 
Useful stabilizers also include tetraphenylverdazyl derivatives wherein 
one or more of the phenyl groups are replaced by substituted phenyl or 
C.sub.1 -C.sub.10 alkyl groups. Another group of useful stabilizers is the 
low molecular weight oximes disclosed in U.S. Pat. No. 4,261,872, Eammons, 
et al., issued Apr. 14, 1981, incorporated herein by reference. Such 
stabilizers may be combined with the catalysts, as defined above, to form 
a stabilized oxidation catalyst system. When used in this way, such 
stabilized systems generally contain from about 0.05% to about 20%, 
preferably from about 1% to about 15%, of the storage stabilizer and from 
about 99.95% to about 80%, preferably from about 85% to about 99%, of the 
oxidation catalyst. Such stabilized oxidation catalysts may also be 
combined with the resin of the present invention to form compositions 
which are stable upon storage in an oxygen-free environment but which 
undergo a controlled free radical polymerization reaction upon exposure to 
oxygen. Such compositions generally contain from about 80% to about 99% of 
the resin component, from about 0.005% to about 2% of the storage 
stabilizer component, and from about 0.05% to about 5% of the oxidative 
catalyst. 
Paint Compositions 
The polymer precursor materials described in the present application are 
especially adapted for use in formulating paint compositions. The 
compositions are applied to the surface, where the polymer precursor 
materials polymerize in situ, forming the paint film. Thus, the key is to 
use a polymer precursor which will polymerize in situ, upon appropriate 
initiation, in an oxygen atmosphere at room temperature. The particular 
polymer precursor (e.g., the nature and amount of its pendant groups), 
initiator or storage stabilizer selected will affect the speed and 
completeness of the in situ polymerization. These paint compositions 
exhibit outstanding aesthetic and performance properties, including volume 
efficiency (solids content as high as 85 to 90%, as compared with 25 to 
50% for commonly-used paints), high levels of surface continuity, stain 
resistance, and durability, as well as strength and resistance to wear. 
The paints may be formulated either as emulsion-based or as solvent-based 
compositions. 
In an emulsion-based paint, the resin is in the form of small discrete 
droplets dispersed in an aqueous phase. Examples of suitable emulsifying 
agents include, but are not limited to, alkanolamides, amine oxides, alkyl 
sulfonates, alkylbenzene sulfonates, ethoxylated alcohols, ethoxylated 
fatty acids, ethoxylated alkyl phenols, ethoxylated and propoxylated 
amines, ethoxylate and propoxylate block copolymers, glycerol esters, 
glycol esters, lanolin-based derivatives, lecithin derivatives, oelfin 
sulfonates, quaternary ammonium surfactants, ethoxylated sorbitan esters, 
ethoxylated alcohol sulfates, ethoxylated alkylphenol sulfates or 
phosphates, alcohol sulfates, fatty acid ester sulfonates, alkylammonio 
acetates, alkylammonio hexanoates, alkylammonio propane sulfonates, and 
fatty acid sulfates. An emulsion-based paint composition comprises: 
(a) from about 10% to about 60%, preferably from about 15% to about 50%, by 
weight, of solid pigment particles; 
(b) from about 15% to about 60%, preferably from about 20% to about 55%, by 
weight, of the film-forming agents described above; 
(c) an amount, preferably from about 0.1% to about 10%, of an oxidative 
catalyst sufficient to cross-link from about 2% to about 60% of the 
pendant groups of said film-forming agent within about 48 hours upon 
exposure to air at a temperature of 20.degree. C.; 
(d) from about 0.5% to about 10%, by weight, of an emulsifying agent or 
agents; 
(e) from 0% to about 25% of an organic cosolvent; and 
(f) the balance water. 
The paint compositions of the present invention are more frequently 
formulated as solvent-based paints. Such solvent based compositions 
comprise: 
(a) from about 10% to about 60%, preferably from about 15% to about 50%, by 
weight, of solid pigment particles; 
(b) from about 15% to about 60%, preferably from about 20% to about 55%, by 
weight, of a film-forming agent as described above; 
(c) an amount, preferably from about 0.1% to about 10%, of an oxidative 
catalyst sufficient to cross-link from about 2% to about 60% of the 
pendant groups of said film-forming agent within about 48 hours upon 
exposure to air at a temperature of 20.degree. C.; and 
(d) from about 5% to about 45%, preferably from about 10% to about 30%, by 
weight, of a solvent for said film-forming agent. 
The paint compositions are formulated in the conventional manner known in 
the art; the particular amounts and components included in any given 
composition being dependent upon such factors as the likely service 
environment of the paint, the desired life expectancy of the coating, the 
method of application, the color, the surface finish, the desired drying 
time and, the desired cost of the formulation. 
Solvents used in the paint compositions are volatile liquids added in order 
to dissolve the resin component and to modify the viscosity of the 
coating. To be effective, the solvent must fultill certain criteria. It 
must yield a solution of viscosity to suit the storage and application 
requirements of the paint. It should have the correct evaporation rate and 
it must deposit a film with optimum characteristics. It should also have 
an acceptable odor, minimal toxicity, and a reasonable cost. In 
formulating a paint with convertible resins, as is the case in the present 
invention, solvents are primarily added to enable the coating to be 
applied by the appropriate technique. The two most important 
characteristics of solvents for use in paint compositions are solvent 
power (ability to dissolve specific resins) and evaporation rate (the 
relative speed with which they leave the coating after application). 
Solvents conventionally known for use in paint compositions are useful in 
the compositions herein; such solvents include, but are not limited to, 
2-ethylhexyl acetate, amyl acetate, ethyl acetate, isobutyl acetate, 
n-propyl acetate, Ektasolve.RTM. DB (diethylene glycol monobutyl ether), 
Ektasolve.RTM. DE acetate (diethylene glycol monoethyl ether acetate), 
Carbitol.RTM. acetate, Cellosolve.RTM. acetate, Texanol.RTM. ester 
alcohol (2,2,4-trimethyl pentanediol-1,3-monoisobutyrate), ethanol, and 
mixtures thereof. Solvents particularly useful in the paint compositions 
of the present invention include ethyl acetate, amyl acetate, propylene 
glycol, mixtures of ethyl acetate and propylene glycol, mixtures of ethyl 
acetate, ethanol and propylene glycol, and mixtures of ethyl acetate, 
propylene glycol and water. 
The paint compositions of the present invention may also, optionally, 
contain a storage stabilizer, as described above, to inhibit the free 
radical polymerization reaction while the paint is stored in its 
container, but permitting the reaction to take place once the paint is 
applied to the surface. Such stabilizers are generally contained in the 
paint compositions in amounts of from about 0.005% to about 5%, by weight, 
of the total composition. A particularly useful storage stabilizer is 
tetraphenylverdazyl, having the formula 
##STR11## 
A pigment, which can be organic or inorganic in origin, may be defined as a 
solid material in the form of small discrete particles, which is 
incorporated into, but remains insoluble in, the paint medium. A pigment 
confers a number of attributes to a paint film, notably color and opacity, 
while influencing the degree of resistance of the film to light, 
contaminants and other environmental factors, as well as modifying the 
flow properties of the liquid paint. Pigments may be either organic or 
inorganic in origin. Inorganic pigments may be conveniently classified by 
color. Those useful in the present invention include white pigments, such 
as titanium dioxide, zinc oxide, antimony oxide, white lead, and basic 
lead sulfate; red pigments, including red iron oxide, red lead, cadmium 
red, and basic lead silicochromate; yellow pigments, including lead 
chromates, zinc chromates, yellow iron oxides, cadmium yellow, and calcium 
plumbate; green pigments, including chromium oxide and lead chrome green; 
blue pigments, such as Prussian blue and ultramarine blue; and black 
pigments, such as black iron oxide. Of course, mixtures of various 
pigments may be used. The pigments are used in combinations and amounts 
based on factors such as color and color intensity desired, intended use 
of the paint, and the identity and properties of other components used in 
the paint formulation. Titanium dioxide, because of its non-toxicity and 
its very high stability, is a particularly preferred pigment for use in 
the paint compositions of the present invention. Metallic pigments useful 
in the present invention include aluminum powder, zinc powder and lead 
powder. Organic pigments which may be used in the paint compositions 
include red pigments, such as toluidine red, and arylamide red; yellow 
pigments, such hansa yellow and benzidine yellow; green pigments, such as 
pigment green D; blue pigments, such as phthalocyanine blue; and black 
pigments, such as carbon black. Pigment extenders (e.g., calcium 
carbonate, silica) may replace part of the pigment used; this is 
especially true where relatively high pigment levels (e.g., 40-60 % of the 
compositions) are being used. 
There is a further class of paint additives that are also insoluble in the 
paint medium but which impart little or no opacity or color to the film 
into which they are incorporated. These materials are known as extenders 
and they are all of inorganic origin. Extenders are incorporated into 
paints to modify the flow properties, gloss, surface topography and the 
mechanical and permeability characteristics of the film. Extenders useful 
in the present invention include barytes, whiting, china clay, mica, and 
talc. 
Dyes are exclusively of organic origin; generally, although not 
necessarily, dyes and organic pigments are only incorporated into paints 
whose prime function is decorative rather than protective. 
Plasticizers may also be included in the paint compositions defined herein. 
The main function of a plasticizer is to increase and maintain film 
flexibility, particularly in paints based on binders which, in the absence 
of plasticization, tend to be brittle. Plasticizers can either be added 
physically to the paint composition, generally during manufacture, or they 
can be chemically incorporated into the polymer molecule by 
copolymerization techniques. Useful plasticizers include dibutyl 
phthalate, dioctyl phthalate, triphenyl phosphate, tricresyl phosphate, 
trichloroethyl phosphate, butyl stearate, and chlorinated paraffins. 
Additional components, conventionally used in paint formulations, may be 
incorporated into the paint compositions of the present invention at their 
art-established usage levels; such components include, but are not limited 
to, drying accelerators; biocides, such as complex compounds of phenol, 
formaldehyde and, less commonly, mercury; fungicides, such as zinc oxide, 
barium metaborate, organomercurials, organotin compounds, 
dithiocarbamates, and dichlorfluamide; antifouling agents, such as 
metallic copper, copper suboxide, tributyl tin oxide and mercuric oxide; 
pigment dispersing agents; paint viscosity modifiers, such as natural 
clays, thixotropic resins, and cellulose ethers; flatting agents; flow 
control agents; anti-sag agents; surface conditioners; yield strength 
agents; and pigment anti-settling agents, such as surface-active agents, 
most notably soya lecithin at levels of 1% of the pigment content. 
Plastic Compositions 
The polymer precursor materials of the present invention are also 
beneficially incorporated into plastic compsitions. Such plastic 
compositions exhibit very high levels of mechanical strength and 
durability. The plastic compositions contain from about 20% to about 99%, 
preferably from about 30% to about 90%, of the polymer precursor materials 
as described above, or of the cross-linked polymers formed from these 
materials. In addition, these compositions may optionally also contain 
from about 0.1% to about 10%, especially from about 0.5% to about 5%, of a 
free-radical polymerization catalyst, especially one which catalyzes the 
free radical polymerization of the resins upon exposure to heat, 
ultraviolet radiation or oxygen. Preferred oxygen-initiated catalysts 
include the mixtures of hydrocarbon compounds with peroxide-decomposing 
transition metal materials, especially cobalt(II) compounds, described 
hereinbefore. The plastic compositions may additionally contain components 
conventionally found in plastics at their art-established usage levels. 
Examples of such components include, but are not limited to, extenders 
(e.g., chopped fiberglass), minerals (e.g., silica), plasticizers, 
anti-oxidants, hardeners, dyes, colorants, opacifiers or compounds to 
modify the mechanical, electrical, thermal, chemical or optical properties 
of the plastic. 
The plastic compositions described herein may be manufactured and used in a 
variety of physical forms for a variety of applications. For example, the 
resins may be polymerized, such as by an injection molding process, and 
used as pre-formed sheets or shaped parts (such as in an automobile or 
boat body). The plastics of the present invention are especially 
well-adapted for use in reaction injection molding processes; such 
processes are described in detail in Milby, Plastics Technology, 
McGraw-Hill, Inc., 1973, pages 334-389, incorporated herein by reference. 
In a reaction injection molding process, the polymer precursor and 
catalyst, in a liquid state, are injected through channels into a closed 
mold. The polymerization reaction is then initiated, and a plastic film in 
the desired configuration is formed. 
In contrast, the resins may be used in the form of a liquid composition 
containing the appropriate catalyst and, if desired, a storage stabilizer. 
The compositions may be applied as a film to, for example, floors or 
automobile exteriors, and will polymerize on exposure to the air forming a 
strong, durable protective coating. 
As used herein, all percentages and ratios given are by weight, unless 
otherwise specified.

The following non-limiting examples illustrate the present invention. 
EXAMPLE I 
Resin Backbone Preparation 
The backbone portion of the precursor materials descibed in the present 
application may be prepared using procedures known in the art. See 
Sorenson and Campbell, Preparative Methods of Polymer Chemistry, 2nd 
Edition, page 154. Methyl acrylates (MA)/hydroxyethyl acrylate (HEA) and 
methyl acrylate/hydroxyethyl acrylate/acrylic acid (AA) backbone polymers 
were made in the following manner, using a high pressure lab 3 gallon 
reactor and the components described in the following table. 
______________________________________ 
Ingredient grams moles ml (21.degree. C.) 
______________________________________ 
9 MA:2HEA 
Methyl Acrylate 3523 40.9 3380 
Hydroxyethyl Acrylate 
1056 9.1 960 
Acrylic Acid -- -- -- 
4579 50.0 4440 
Ethyl Acetate 6608 75.0 7340 
Dodecyl Mercaptan (DDM) 
324 1.6 
Azobisisobutyronitrile 
41.1 0.25 
(AIBN) 
8 MA:3HEA:1AA 
Methyl Acrylate 2870 33.3 2990 
Hydroxyethyl Acrylate 
1451 12.5 1320 
Acrylic Acid 300 4.2 287 
9621 50.0 4597 
Ethyl Acetate 6608 75.0 7340 
Dodecyl Mercaptan (DDM) 
324 1.6 
Azobisisobutyronitrile 
41.1 0.25 
(AIBN) 
______________________________________ 
The reactor was first checked for water flow to the coil, jacket and 
condenser. The reactor was then purged with nitrogen for 1 to 2 minutes. 
Condenser water was turned on and ingredient addition was begun. Half of 
the ethyl acetate was charged into the reaction flask and the mixer was 
started. The monomers were then added in the following order: MA, HEA, AA. 
Residual monomer was washed into the reaction vehicle using ethyl acetate. 
Next, DDM was added to the reaction mixture, followed by AIBN which was 
washed into the reactor with the remainder of the ethyl acetate. The 
reactor was heated to 49.degree. C., and, since the reaction is 
exothermic, the temperature was allowed to rise to 60.degree. C. The 
temperature of the reaction flask was then maintained at 60.+-.3.degree. 
C. by adjusting the coil cooling water. When the reaction was complete 
(about 1 hour), the reactor was heated to 75.5.+-.2.degree. C. and 
maintained at that temperature for 4 to 6 hours to decompose the AIBN. The 
reactor was then cooled to room temperature and the reaction mixture was 
removed. The molecular weight of the resin backbone formed ranges from 
about 2,000 to about 8,000 and can be controlled by adjusting the level of 
DDM in the reaction mixture. 
Capping Reaction of 9MA:2HEA Backbone Resin with Beta Vinyl Itaconyl 
Chloride 
The 9MA:2HEA backbone resin, synthesized above, was capped, using beta 
vinyl itaconyl chloride (B-VIC), to form a preferred resin material 
described in the present application. B-VIC was synthesized via the 
transvinylation of itaconic acid with vinyl acetate; this process is 
described in concurrently-filed U.S. Patent Application Ser. No. 290,907, 
Bush, 4-Vinyl-2-Methylenebutanedioic Acid Compounds, incorporated herein 
by reference. The reaction and reagents utilized in that procedure are 
described in the following table. 
______________________________________ 
##STR12## 
##STR13## 
##STR14## 
(C.sub.2 H.sub.5).sub.3 N.HCl 
Reagent Function Amount Moles 
______________________________________ 
(9MA:2HEA) 
backbone 96g. solids 0.19 (moles OH) 
B-VIC 
capping group 
33g. 0.19 
Ethyl Acetate 
solvent 500 ml. 5.7 
Triethylamine 
base catalyst 
19g. 0.19 
______________________________________ 
(A) = mixed acrylates 
A two-liter, three-neck round-bottom flask was fitted with the following: a 
Teflon stirring paddle, shaft and bearing for an overhead mechanical 
stirrer; a 250 milliliter addition funnel with a side arm; an argon inlet 
at the top of the addition funnel; a thermometer; and an argon outlet 
attached to a bubbler. 
The flask was flushed with argon and an argon atmosphere maintained during 
the reaction. The backbone resin in ethyl acetate, B-VIC, and ethyl 
acetate solvent were placed in the reaction flask. Vigorous stirring was 
begun and the drop-wise addition from the addition funnel of a solution of 
distilled triethylamine in an equal amount of ethyl acetate was begun. The 
triethylamine was distilled through a 12-inch Vigreux column at 
atmospheric pressure and the middle cut, boiling at 80.degree. C., was 
used. To promote good mixing and dispersion of the triethylamine and to 
prevent gellation, it is important that the addition of this solution be 
slow. The addition step took about 2 hours. During the addition of the 
triethylamine, the amine hydrochloride formed precipitated as a white 
solid, giving the reaction mixture a white cloudy appearance. Toward the 
end of the addition, a more muddy appearance developed as the reaction 
mixture darkened. At this point, if the color becomes intense, the 
addition of triethylamine solution should be stopped. After the 
triethylamine addition is stopped or completed, the reaction should be 
worked up immediately. 
The precipitated amine hydrochloride was filtered through a Buchner funnel 
with Whatman glass fiber paper using a lab aspirator (about 20 mm 
mercury). The filtration proceeded rapidly. The filter cake was then 
washed with 100 milliliters of ethyl acetate. A 10 milliliter aliquot of 
the ethyl acetate filtrate was concentrated on a rotovap and was used for 
an NMR spectrum. The rest of the solution was transferred to a 2 liter 
separatory funnel and washed with an equal volume of saturated sodium 
bicarbonate solution. An emulsion was formed and several hours was 
required for a clean, distinct separation of phases. The mixture was 
allowed to stand overnight to separate. The lower layer still contained 
some insoluble polymer, but was easily separated from the upper layer. The 
lower layer consisted of the aqueous phase which was drawn away and 
discarded. The upper organic phase was drawn into a 2 liter Erlenmeyer 
flask and 100 grams of anhydrous magnesium sulfate was added and allowed 
to stand for half an hour. The magnesium sulfate was then filtered out 
through a Buchner funnel with glass fiber paper. The resulting ethyl 
acetate solution was then concentrated on a rotovap (H.sub.2 O) aspirator, 
2 mm mercury, 40.degree. C.) to the desired solids level, approximately 
75-85% solids. The solids level was determined by the following ASTM 
method of evaporation at 100.degree. C. for two hours: a sample of the 
concentrated resin was accurately weighed (to 4 decimal places) into a 
glass Petri dish, placed in the oven at 100.degree. C. for two hours, 
cooled to room temperature and reweighed. 
The resin was transferred to a bottle and stored under argon at 0.degree. 
C. It is important that oxygen be excluded to prevent premature 
polymerization of the resin. The product was then analyzed by NMR (in 
CDCl.sub.3) and IR (neat with residual ethyl acetate). In the infrared 
spectrum, the vinyl group is seen at 1640 cm.sup.-1. The NMR spectrum 
showed the following peaks (chemical shifts reported in .delta.): 
______________________________________ 
1.73 two broad peaks for the hydroxy ethyl acrylate 
2.33 portion of the backbone 
3.47 
##STR15## 
3.67 singlet 3H, (CO.sub.2 CH.sub.3).sub.9 
##STR16## 
##STR17## 
4.53 
4.63 
4.73 doublets 2H, CHCH.sub.2 
5.00 
5.83 6.37 
##STR18## 
7.03 
7.13 
7.27 quartet 1H, CHCH.sub.2 
7.37 
______________________________________ 
Capping Reaction of 9MA:2HEA Backbone Resin with Beta Allyl Itaconyl 
Chloride 
As in the previous procedure, the 9MA:2HEA backbone was capped using beta 
allyl itaconyl chloride to form a preferred resin material. The reagents 
described in the following table were reacted in the manner of the 
previous procedure: 
______________________________________ 
##STR19## 
##STR20## 
Reagent Function Amount Moles 
______________________________________ 
9MA:2HEA 
backbone 318 g solids 
0.64 (Moles OH) 
Beta-AIC 
capping group 
120 g 0.65 
Ethyl acetate 
solvent 1 l. 10.2 
Triethylamine 
catalyst 64 g 0.64 
______________________________________ 
After work-up in the manner of the previous procedure and rotovapping to 
the desired solids level (approximately 75-85% solids), the resin was 
transferred to a bottle and stored under argon at 0.degree. C. The 
identity of the resin was confirmed by NMR and IR spectra. 
Capping Reaction of (8MA:3HEA:1AA) Backbone Resin with Beta Vinyl Itconyl 
Chloride 
A preferred resin of the present application was synthesized using 
8MA:3HEA:1AA backbone resin, synthesized above, and beta vinyl itaconyl 
chloride, using the procedure described below; the reaction and reagents 
used in the reaction are given in the following table. 
______________________________________ 
##STR21## 
##STR22## 
Reagent Function Amount Moles 
______________________________________ 
(8MA:3HEA:1AA) 
backbone 50 g. solids 
0.135 
(moles OH) 
B-VIC 
capping group 23.5 g. 0.135 
Ethyl acetate 
solvent 200 ml. 2.3 
*Amberlyst A-21 
ion exchange 
resin to 
take up acid 64 g. 0.27 
(dry resin) 
Triethylamine (TEA) 
catalyst 0.68 g. 0.0068 
______________________________________ 
*Amberlyst A21 (available from Rohm & Haas) is a weakly basic anionic 
exchange resin intended for the absorption of acidic solutes from either 
aqueous or nonaqueous media. The resin is furnished in the hydrated, 
freebase form and the water must be removed or replaced with ethyl acetat 
prior to use. 
A one-liter 3-neck round-bottom flask was fitted with the following: a 
Teflon stirring paddle, shaft and bearing for an overhead mechanical 
stirrer; a 250-milliliter addition funnel with a side arm; an argon inlet 
at the top of the addition funnel; a thermometer; and an argon outlet 
attached to a bubbler. 
The ion exchange resin was conditioned by treating it with several volumes 
of methanol in a column, allowing the methanol to pass down at a flow rate 
of 4 bed volumes per hour. Further conditioning of the methanol-moist 
resin was then performed by passing several volumes of ethyl acetate 
through the resin bed at the same flow rate. The resin was used wet in the 
ethyl acetate solution, although it may also be used in a dry state. In 
either case, it is imperative that no methanol remain in the resin, due to 
its reactivity with beta vinyl itaconyl chloride. If it is desired to use 
dry resin, the ethyl acetate solvent may be removed using reduced pressure 
on a rotovap at a temperature less than 75.degree. C. 
The flask was flushed with argon and an argon atmosphere was maintained 
during the reaction. The backbone resin in ethyl acetate, the ion exchange 
resin, triethylamine catalyst and the ethyl acetate solvent were placed in 
the reaction flask. Vigorous stirring was begun and a solution of B-VIC in 
an equal volume of ethyl acetate was added dropwise to the reaction vessel 
from the addition funnel. The addition required about 15 to 30 minutes. At 
the end of the addition, the reaction was slightly exothermic (about 
35.degree. C.). 
The reaction mixture was allowed to stir at room temperature under argon 
for an additional 3 hours and was then worked up in the following manner. 
The ion exchange resin was filtered through a Buchner funnel with glass 
fiber paper and washed with 200 milliliters of ethyl acetate. A 10 
milliliter aliquot of the ethyl acetate filtrate was concentrated on a 
rotovap and used for an NMR spectrum. The rest of the solution was 
transferred to a one liter separatory funnel and washed with an equal 
volume of saturated sodium bicarbonate solution. An emulsion, which 
required several hours to form a clean, distinct separation of phases, 
resulted. The mixture was allowed to stand overnight to separate. The 
lower layer contained some insoluble polymer, but was easily separated 
from the upper layer. The lower layer (the aqueous phase) was drawn away 
and discarded. The upper organic phase was drawn into a one liter 
Erlenmeyer flask and 100 grams of anhydrous magnesium sulfate were added 
and allowed to stand for one half hour. The magnesium sulfate was then 
filtered out through a Buchner funnel with glass fiber paper. The 
resulting ethyl acetate solution was concentrated on a rotovap (H.sub.2 O 
aspirator, 20 mm mercury, 40.degree. C.) to the desired solids level, 
approximately 75-85% solids. The solids level was determined by the 
following ASTM method of evaporation at 100.degree. C. for two hours: a 
sample of the concentrated resin was accurately weighed (to 4 decimal 
places) into a glass Petri dish, placed in an oven at 100.degree. C. for 
two hours, cooled to room temperature and reweighed. 
The resin was then transferred to a bottle and stored under argon at 
0.degree. C. It is important that oxygen be excluded to prevent premature 
polymerization. The identity of the resin formed was confirmed by NMR and 
IR spectra. 
EXAMPLE II 
Using conventional procedures known in the art (see Sorenson and Campbell, 
Preparative Methods of Polymer Chemistry, 2nd Edition, page 154) and the 
techniques described in Example I, additional resin materials of the 
present invention were synthesized as described below. 
A poly(ethylene-co-trimethylolpropylene adipate) backbone resin was 
synthesized as follows. The reaction flask was charged with 305 grams 
adipic acid, 22.4 grams trimethylolpropane, 186 grams ethylene glycol and 
8.6 grams p-toluenesulfonic acid monohydrate. The mixture was heated at 
120.degree. C., under an argon atmosphere, overnight; 90 milliliters of 
water were collected in a Dean Stark trap. The resulting polyester 
backbone was analyzed for hydroxyl and carboxyl end groups by titration. 
Similarly, a poly(ethylene-co-pentaerythritol adipate) backbone was 
synthesized in the following manner. The reaction flask was charged with 
8.5 grams pentaerythritol, 93 grams ethylene glycol, 153 grams adipic acid 
and 4.3 grams p-toluenesulfonic acid. The mixture was heated at 
120.degree. C., under argon, until the distillation of water ceased. 
Vinyl itaconate-capped polyesters of the present invention can be prepared 
from the backbones synthesized above by either of two methods: (a) 
addition of itaconic anhydride to the backbone, forming the acid 
intermediate, followed by transvinylation with vinyl acetate; or (b) a 
more direct route by acylation with vinyl itaconyl chloride of the free 
hydroxyls on the backbone resin. For example, according to route (a), 199 
grams poly(ethylene-co-pentaerythritol adipate) polyester backbone, 52 
grams itaconic anhydride and 200 milligram hydroquinone were heated at 
90.degree. C., under argon, for three hours. To the reaction flask was 
added 700 milliliters vinyl acetate, 5 grams mecuric acetate and 1 gram 
concentrated sulfuric acid. Refluxing was continued for 21/2 hours and the 
final reaction mixture was worked up according to conventional methods. 
Polycarbonate backbone resins may be prepared by conventional methods from 
bisphenols or diols and phosgene or in a melt polycondensation with 
diphenyl carbonate. For example, equal molar quantities of bisphenol A (25 
grams) and diphenyl carbonate (24 grams) were mixed under argon and heated 
at 140.degree. C. until the distillation of phenol ceased. A vacuum was 
then applied to remove residual phenol. 
Another polycarbonate backbone was prepared by mixing 78 grams 
hexamethylene glycol, 72 grams diethyl carbonate and 0.25 grams sodium and 
heating them at 110.degree. C., under argon, until the distillation of 
ethanol ceased. The vinyl itaconate-capped resin of the present invention 
was then prepared from this backbone material using the itaconic 
anhydride-vinyl acetate route, described above. 
Mixed acrylate backbones were also prepared using the same procedure 
described for preparing methyl acrylate resins in Example I. The capping 
reaction with vinyl itaconate was also carried out in the manner described 
in Example I. Using this procedure, the following backbone resins were 
prepared: 9 ethyl acrylate: 2 hydroxyethyl acrylate: 1 acrylic acid; 9 
butyl acrylate: 2 hydroxyethyl acrylate: 1 acrylic acid; and 14 methyl 
methacrylate: 3 hydroxyethyl acrylate: 3 acrylic acid. By way of example, 
the (14 MMA:3HEA:1AA) vinyl itaconate resin of the present invention was 
prepared as follows. The backbone resin was synthesized using the 
procedure described in Example I by reacting 50 grams methyl methacrylate, 
12.5 grams 2-hydroxyethyl acrylate, 7.7 grams acrylic acid, 1 gram AIBN, 2 
grams dodecanethiol and 50 milliliters ethyl acetate. This backbone resin 
was then capped using an excess of alpha-vinyl itaconyl chloride in ethyl 
acetate with an equal molar amount of calcium carbonate base, as described 
in Example I. 
EXAMPLE III 
High solids, solvent-based paint formulae of the present invention, having 
the compositions given below, were prepared in a conventional manner. The 
resin, titanium dioxide, silica and ethyl acetate components were 
thoroughly mixed together in a Cowles or flat blade mixer until the 
components were well dispersed. The initiator system, i.e., the 
hydrocarbon peroxide precursor and cobalt(II) compound, were then added 
into the composition and mixed and dispersed gently. The flatting agent 
may be added to the initial mixture or to the dispersed mixture before the 
initiator is added. The compositions, below, provided high solids paint 
compositions which exhibited excellent covering characteristics, strength 
and durability. 
______________________________________ 
Component parts (by weight) 
______________________________________ 
Composition A 
(8MA:3HEA:1AA) vinyl itaconate 
35 
TiO.sub.2 (Rutile) 30 
Amorphous silica 5 
Micron-sized silica flatting agent 
5 
Ethyl acetate 23 
1,3-bis(1,3-dioxolan-2-yl)propane 
2 
Cobalt naphthenate 0.1 
Composition B 
(9MA:2HEA) vinyl itaconate 
25 
TiO.sub.2 (Rutile) 40 
Amorphous silica 5 
Flatting agent (silica) 
5 
Ethyl acetate 23 
1,3-bis(1,3-dioxolan-2-yl)propane 
2 
Cobalt naphthenate 0.1 
Composition C 
(8MA:3HEA:1AA) vinyl itaconate 
35 
TiO.sub.2 30 
Amorphous silica 5 
Flatting agent (silica) 
5 
Ethyl acetate 8 
Ethanol 8 
Propylene glycol 7 
1,3-bis(1,3-dioxolan-2-yl)propane 
2 
Cobalt naphthenate 0.1 
Composition D 
(9MA:2HEA) vinyl itaconate 
30 
TiO.sub.2 30 
Calcium carbonate 5 
Amorphous silica 5 
Flatting agent (silica) 
5 
Ethyl acetate 23 
1,3-bis(1,3-dioxolan-2-yl)propane 
2 
Cobalt naphthenate 0.1 
______________________________________ 
Substantially similar results are obtained where the resin materials 
contained in the above compositions are replaced, in whole or in part, by 
(8MA:3HEA:1AA) vinyl itaconate, (9MA:2HEA)vinyl itaconate, 
poly(ethylene-co-trimethylolpropylene adipate) vinyl itaconate, 
poly(ethylene-co-pentaerythritol adipate) vinyl itaconate, 9 ethyl 
acrylate:2 hydroxyethyl acrylate:1 acrylic acid vinyl itaconate, 9 butyl 
acrylate:2 hydroxyethyl acrylate:1 acrylic acid vinyl itaconate, 14 methyl 
methacrylate:3 hydroxyethyl acrylate:3 acrylic acid vinyl itaconate, 
(9MA:2HEA) beta-allyl itaconate, or resins having backbones as previously 
described and wherein the pendant groups are selected from mono-methyl 
itaconate, 4-allyl-2-methylenesuccinate, 1 -vinyl-2-methylenesuccinate, 
p-vinylbenzoic acid, mono-vinyl maleate, methyl methacrylate, 
N-phenyl-2-methylenesuccinimide and substituted 
N-phenyl-2-methylenesuccinimides. 
Substantially similar results are also obtained when the titanium dioxide 
pigment component in the above compositions is replaced, in whole or in 
part, by zinc oxide, antimony oxide, white lead, basic lead sulfate, red 
iron oxide, red lead, cadmium red, basic lead silicochromate, lead 
chromate, zinc chromate, yellow iron oxide, cadmium yellow, calcium 
plumbate, chromium oxide, lead chrome green, Prussian blue, ultramarine 
blue, black iron oxide, aluminum powder, zinc powder, lead powder, 
toluidine red, arylamide red, hansa yellow, benzidine yellow, pigment 
green D, phthalocyanine blue, carbon black, and mixtures thereof. 
Similar results are also obtained wherein the hydrocarbon peroxide 
precursor contained in the above compositions is replaced, in whole or in 
part, with 
##STR23## 
or mixtures thereof. 
Similar results also obtained where the cobalt naphthenate in the above 
compositions is replaced, in whole or in part, with cobalt(II) 
dipivaloylmethane, cobalt(II) acetylacetonate, cobalt(II) acetate, 
cobalt(II) decanoate, and mixtures thereof. 
The compositions described above may also contain an effective amount of a 
storage stabilizer component, such as from about 0.1 to about 1% of 
tetraphenyl verdazyl. 
EXAMPLE IV 
An emulsion-based paint formulation of the present invention was prepared 
in the following manner. 
Part 1: 
6.7 grams (8MA:3HEA:1AA) vinyl itaconate (about 85% solids) 
6.7 grams TiO.sub.2 
1.8 grams propylene glycol 
0.2 gram AMP-95 (2-amino-2-methyl-1-propanol, available from IMC 
Corporation) 
The above components were mixed well with a flat blade high speed mixer. 
Part 2: 
7.2 grams water 
0.9 gram carbitol acetate (diethylene glycol monoethyl ether acetate) 
0.5 gram nopcosperse 44 (dispersant for TiO.sub.2 in aqueous systems, 
available from Diamond Shamrock) 
0.1 gram DM-710 Igepal (dinonylphenoxypoly(ethyleneoxy)ethanol nonionic 
surfactant commercially available from GAF Corp.) 
0.05 gram DM-880 Igepal (dinonylphenoxypoly(ethyleneoxy)ethanol nonionic 
surfactant commercially available from GAF Corp.) 
The components of part 2 were mixed until all the surfactants were 
dissolved. Then, part 3, below, was added to part 2 in small portions with 
stirring; the stirring was continued until the mixture was well dispersed. 
Part 3: 
4 grams TiO.sub.2 
The part 2 plus part 3 mixture was then added gradually to part 1, with 
stirring, the stirring continuing until a homogenous mixture was formed. 
Finally, the initiator system (a mixture of about 0.5 part 
1,3-bis(1,3-dioxolan-2-yl)propane and 0.025 part cobalt naphthenate) was 
mixed into the emulsion. 
The emulsion paint formed by this procedure exhibits excellent covering 
qualities, is high in solids, and is strong and durable under heavy wear 
conditions. 
An additional emulsion-based paint formulation of the present invention was 
formulated as follows: 
Part 1: 
10 grams 9MA:2HEA capped with allyl itaconate (70% solids) 
0.1 grams ethoxylated sorbitan monoleate (20 ethoxylate groups per sorbitan 
monoleate--Tween 80) 
0.45 grams cobalt naphthenate (6% cobalt, from Sheppard Chemical Co.) 
0.54 grams Lupersol 256 (2,5-dimethyl-2,5-bis(2 ethyl 
hexanoylperoxy)hexane, Pennwalt Lucidal Co.) 
These ingredients were brought to homogeneous solution. 
4.0 grams of 1% aqueous polyethoxy-polypropoxy block copolymer (Pluronic 
F87, Wyandotte BASF Co.) was added, and emulsified with high shear mixing. 
Part 2: 
6 grams titanium dioxide 
5 grams 1% aqueous Pluronic F-87 
In forming part 2, the TiO.sub.2 was blended into the aqueous Pluronic 
solution until a smooth mixture resulted. 
Part 2 was then added to Part 1 slowly and with hand stirring until 
transfer was complete, then the composition was subjected to high shear 
mixing until uniform. 
EXAMPLE V 
A paint composition, having the components listed below, was formulated 
according to the method described in Example III. This paint was then 
compared with a commercial latex paint (i.e., Sears Easy Living.RTM. 
paint) to determine their comparative properties. 
______________________________________ 
Component Weight % 
______________________________________ 
(8MA:3HEA:1AA) vinyl itaconate 
35 
TiO.sub.2 40 
Ethyl acetate 22 
1,3-bis(1,3-dioxolan-2-yl)propane 
2 
Cobalt naphthenate 1 
______________________________________ 
When applied to a wall and permitted to dry, the surface formed by the 
paint of the present invention was smooth and continuous, whereas the 
surface of the commercial paint was characterized by spaces in the matrix 
and the particulate nature of the latex. This was very clearly seen when 
the two surfaces were viewed by scanning electron microscope at a 
magnification of 500X. This difference in film continuity carries over 
into the macroscopic properties of enhanced durability, water resistance 
and decreased permeability for the paint of the present invention. 
The paint of the present invention was compared to the commercial paint in 
terms of stain resistance, using alkaline cleaners, on a representative 
variety of stains using the following procedure. 
The paints were applied, using a thin film applicator, on 61/2 inch by 17 
inch scrub test panels so that the dried film thickness was about 2 mils. 
The films were allowed to air dry and cure for one week. Stains were then 
applied to each painted panel in a 21/2 inch strip widthwise across the 
panel in the center of the dry paint film. Quantities and types of stains 
applied were as follows: (a) oil stain--30 drops from a Pasteur pipette; 
(b) crayon stain--red Crayola.RTM. crayon--21/2 inch band at 200 gram 
pressure; (c) High Point.RTM. instant coffee (0.2 gram); (d) French's.RTM. 
mustard (0.2 gram); (e) ballpoint pen ink, Bic.RTM. (21/2 inch band, 200 
gram pressure); (f) aluminum mar (21/2 inch band, 200 gram pressure. The 
stains were allowed to set for 15 minutes. Using a Gardner colorimeter, 
model XL-23, the L,a,b and Hunter whitness of both stained and unstained 
paint portions were made. The samples were then placed in a scrub machine 
having a large sponge holder. The sponge was moistened and squeezed by 
hand and then was wet with 15 milliliters of a cleaning solution made up 
of Mr. Clean.RTM., commercially available from The Procter & Gamble 
Company, in distilled water (weight ratio of cleaner:water=1:64). On each 
sample the machine was permitted to run 5 cycles back and forth. The 
Hunter whiteness readings of the paint samples were then read again and 
were compared to the prescrub readings. 
Using this procedure, the paint composition of the present invention showed 
a significant stain removal advantage vs. the commercial paint over the 
range of soils tested. Because the paint of the present invention provides 
a more continuous film, the staining substances cannot penetrate the 
surface and become entrapped, as they can in latex paint; therefore, 
stains remain only on the surface of the paint of the present invention 
and stain removal is greatly enhanced. 
The paint composition of the present invention also provided significant 
advantages over the commercial paint in mar resistance, hardness and 
impact tests using ASTM-established test procedures. Durability advantages 
were seen in the improved washability (the paint compositions of the 
present invention outscrubbed the commercial paint by 3 to 4 times in ASTM 
scrub tests), and in excellent chemical resistance (i.e., the paint 
compositions of the present invention were not removed by organic 
solvents, such as acetone, or by full-strength alkaline cleaners). 
EXAMPLE VI 
Plastic compositions incorporating the technology of the present invention 
are illustrated by the following formulations. 
______________________________________ 
Component Weight % 
______________________________________ 
(8MA:3HEA:1AA) vinyl itaconate 
75 
1,3-bis(1,3-dioxolan-2-yl)propane 
4 
cobalt naphthenate 2 
miscellaneous components (e.g., plasticizer, 
balance 
colorant tetraphenyl verdazyl storage 
stabilizer, extender) 
______________________________________ 
The components in the above table are combined, using conventional mixing 
and dispersion techniques, to form a plastic precursor material. This 
material may be sold as is, to be formed or molded by the purchaser into 
plastic sheets or molded plastic parts. The plastic formed exhibits very 
high strength and durability characteristics. The oxygen-initiated 
catalyst system in the above composition may be replaced by a 
heat-initiated catalyst system, and the composition may then be used in a 
conventional injection molding process to form shaped plastic articles. 
Obviously, the above composition may also be preformed into sheets or 
molded plastic articles and may be sold or used in that form. In that case 
composition of the articles is essentially the same as that given in the 
table except that the vinyl itaconyl resin precursors have reacted to form 
cross-linked polymers. 
______________________________________ 
Component Weight % 
______________________________________ 
(9MA:2HEA) vinyl itaconate 
40 
1,3-bis(1,3-dioxlan-2-yl)propane 
3 
cobalt naphthenate 0.15 
tetraphenyl verdazyl 0.1 
ethyl acetate 50 
miscellaneous components (e.g., hardener, 
balance 
anti-oxidant, sheeting agent) 
______________________________________ 
The components described in the above table may be combined using 
conventional mixing and dispersion techniques to form a plastic coating 
composition. This composition may be applied to, for example, floors or 
automobile bodies in a thin coat, polymerizing upon exposure to oxygen, 
forming a strong and durable transparent protective coating on the 
surface. 
In either of the above plastic compositions, the hydrocarbon component of 
the catalyst system may be replaced, in whole or in part, by 
##STR24## 
and mixtures thereof. 
In addition, the cobalt naphthenate, in either of the above compositions 
can be replaced, in whole or in part, by cobalt(II) dipivalolylmethane, 
cobalt(II) acetylacetonate, cobalt(II) acetate, cobalt(II) decanoate, and 
mixtures thereof. 
The resin material used in either of the above two plastic compositions may 
be replaced, in whole or in part, by (8MA:3HEA:1AA) vinyl itaconate, 
(9MA:2HEA) vinyl itaconate, poly(ethylene-co-trimethylolpropylene adipate) 
vinyl itaconate, poly(ethylene-co-pentaerythritol adipate) vinyl 
itaconate, 9 ethyl acrylate: 2 hydroxyethyl acrylate: 1 acrylic acid vinyl 
itaconate, 9 butyl acrylate: 2 hydroxyethyl acrylate: 1 acrylic acid vinyl 
itaconate, 14 methyl methacrylate: 3 hydroxyethyl acrylate: 3 acrylic acid 
vinyl itaconate; (9MA:2HEA)beta-allyl itaconate; or polymer precursor 
materials having the backbones given above but wherein the pendant group 
is replaced, in whole or in part, by mono-methyl itaconate, 
1-vinyl-2-methylenesuccinate, 4-allyl-2-methylenesuccinate, p-vinylbenzoic 
acid, mono-vinyl maleate, methyl methacrylate, 
N-phenyl-2-methylenesuccinimide, substituted 
N-phenyl-2-methylenesuccinimides, or mixtures thereof.