Non-aqueous dispersions based on capped stabilizers and vinyl monomers I

Crosslinked, preferably acrylic, polymer particles characterized in that the particles formed by free radical addition polymerization of: PA1 (a) between about 0.8 and about 20 weight percent each of first and second ethylenically saturated monomers each bearing functionality capable of crosslinking reaction with the other; and PA1 (b) between about 98.4 and about 60 weight percent of at least one other monoethylenically unsaturated monomer; in the presence of (I) an organic liquid which is a solvent for the polymerizable monomers, but a non-solvent for the resultant polymer, and (II) polymeric dispersion stabilizer containing at least two segments with one segment being solvated by the organic liquid and the second segment being of different polarity than the first segment and relatively insoluble in the organic liquid, wherein the reaction is carried out at elevated temperatures such that the dispersion polymer forms and then is crosslinked, wherein the percursor of the first segment of the stabilizer comprises a long chain hydrocarbon molecule having only one reactive group per molecule.

Reference is made to commonly assigned related applications Ser. No. 
455,696 entitled "Non-aqueous Dispersions Based on Capped Stabilizers and 
Reactants Comprising Polyfunctional Monomers II", Ser. No. 455,687 
entitled "Non-aqueous Dispersions Based on Capped Stabilizers and Vinyl 
Monomers II". and Ser. No. 455,701, entitled "Non-aqueous Dispersions 
Based on Capped Stabilizers and Reactants Comprising Polyfunctional 
Monomers I", all to Theodore et al and filed on Jan. 5, 1983. Further 
referencre is made to commonly assigned related U.S. applications, Ser. 
No. 468,901 entitled "Preparation of Non-aqueous Dispersions with use of 
Monofunctional Stabilizer" to Chattha et al., Ser. No. 468,902 entitled 
"Crosslinked Flow Control Additives for High Solids Paints II" to Chattha, 
and Ser. No. 468,912 entitled "Crosslinked Flow Control Additives for High 
Solids Paints I" to Cassatta et al, all filed Feb. 23, 1983. 
TECHNICAL FIELD 
This invention relates to stable, crosslinked polymer particles and 
non-aqueous dispersions containing such particles. More particularly, the 
invention relates to such stable crosslinked, preferably acrylic, polymer 
particles prepared in the presence of a polymeric dispersion stabilizer 
wherein the precursor of the first segment of the stabilizer comprises a 
long chain hydrocarbon molecule having only one reactive group per 
molecule, preferably being a carboxyl group and additionally preferably 
being present as a terminal reactive group on the molecule. 
BACKGROUND ART 
Suitable crosslinked acrylic polymer particles of the type which may employ 
the stabilizer of this invention are well known. U.S. Pat. No. 4,147,688 
to Makhlouf et al teaches crosslinked dispersions wherein crosslinked 
acrylic polymer microgel particles are formed by free radical addition 
polymerization of alpha, beta ethylenically unsaturated monocarboxylic 
acids, at least one other copolymerizable monoethylenically unsaturated 
monomer and a certain percentage of crosslinking monomer, in the presence 
of a hydrocarbon dispersing liquid (See abstract, examples and claims). 
Other crosslinked dispersions containing microgel particles are disclosed 
in the patent application and patents referred to in the Makhlouf et al 
disclosure. 
U.S. Pat. No. 4,025,474 to Porter et al discloses a polyester based coating 
composition which includes the crosslinked dispersions disclosed by 
Makhlouf et al. U.S. Pat. No. 4,075,141 to Porter et al discloses 
carboxylic acid amide interpolymer-based coating compositions including 
the same crosslinked dispersions. U.S. Pat. No. 4,115,472 also to Porter 
et al, discloses urethane coating compositions also including the 
crosslinked dispersions of Makhlouf et al. U.S. Pat. No. 4,055,607 to 
Sullivan et al discloses thermosetting compositions of (a) solution 
acrylic polymer, (b) at least 0.5% of microgel particles formed by 
polymerizing hydroxyl bearing monomers with nonhydroxyl bearing monomers 
in the presence of the stabilizer disclosed by Makhlouf et al, and (c) 
melamine resin. The microgel dispersion of Sullivan et al thus contains 
functionality capable of reacting with the melamine crosslinking agent. 
The dispersion stabilizer employed in producing the microgel particles of 
the Makhlouf et al compositions are generally polymeric and contain at 
least two segments, with one segment being solvated by the dispersion 
liquid and the second segment being of different polarity than the first 
segment, and relatively insoluble, compared to the first segment, in the 
dispersing medium. Included among the dispersion stabilizers referred to 
in the Makhlouf et al patent are polyacrylates and methacrylates, such as 
poly (lauryl) methacrylate and poly (2-ethylhexylacrylate); diene polymers 
and copolymers such as polybutadiene and degraded rubbers; aminoplast 
resins, particularly high naphtha-tolerant compounds such as melamine 
formaldehyde resins etherified with higher alcohols (e.g., alcohols having 
4 to 12 carbon atoms); and various copolymers designed to have desired 
characteristics (see Col. 5, lines 1-27). 
Among the numerous dispersion stabilizers, which could be employed in 
compositions of Makhlouf et al and to which the particular stabilizer 
precursor of this invention may be applied, are those taught by U.S. Pat. 
No. 3,607,821 to Clarke. Clarke teaches a stabilizer for non-aqueous 
dispersions wherein the stabilizer is chemically reacted with dispersed 
particles of the dispersion (Col. 1, lines 36-42). Each co-reactant 
stabilizer molecule forms from 1 to 10 (preferably 1 to 4) covalent links 
with the dispersed polymer (Col. 1, lines 50-52). The covalent links 
between the stabilizer and the dispersed polymer are formed by reaction 
between chemical groups provided by the stabilizer and complementary 
chemical groups provided by the dispersed polymer or by copolymerization 
reaction (Col. 1, lines 63-67). 
Particularly preferred dispersion stabilizers of Makhlouf et al and the 
general type of stabilizer employed in the preparation of particles of 
this invention are those which are graft copolymers comprising two 
polymeric segments with one segment being solvated by the dispersion 
liquid and not associated with polymerized particles of the polymerizable 
ethylenically unsaturated monomers and the second segment being an anchor 
polymer of different polarity from the first type and relatively 
non-solvatable by the hydrocarbon solvent and capable of anchoring with 
the polymerized particles of the ethylenically unsaturated monomer. This 
anchor polymer segment contains pendant groups capable of copolymerizing 
with the ethylenically unsaturated monomer used to form the particles of 
the dispersion (See Col. 5, lines 28-40 of Makhlouf et al). 
DISCLOSURE OF THE INVENTION 
The crosslinked stable polymer particles of this invention applies are 
those which are characterized in that the particles are formed by addition 
polymerization of (a) between about 0.8 and about 20 weight percent each 
of first and second ethylenically unsaturated monomers each bearing 
functionality capable of crosslinking reaction with the other and (b) 
between about 98.4 and about 60 weight percent at least one other 
monoethylenically unsaturated monomer, in the presence of (I) organic 
liquid which is a solvent for the polymerizable monomers, but a 
non-solvent for the resultant polymer, and (II) a polymeric dispersion 
stabilizer. The polymeric dispersion stabilizer as described above in the 
discussion of the prior art, in its broadest sense contains at least two 
segments, with one segment being solvated by the organic liquid and the 
second segment being of different polarity than the first segment and 
relatively insoluble in the organic liquid. The crosslinked dispersion is 
prepared by carrying out the addition polymerization at an elevated 
temperature such that the dispersion polymer is first formed and then 
crosslinked. 
In this invention the precursor of the first segment of the stabilizer is 
characterized in that it comprises a long chain hydrocarbon molecule 
having only one reactive group per molecule, preferably, additionally 
being present as a terminal reactive group on the molecule. 
This invention is also directed to non-aqueous dispersions containing such 
particles and paint compositions employing such particles, e.g., as flow 
control agents. 
One of the serious disadvantages of the aforementioned prior art systems of 
particle formation is the inherent restriction placed on the selection of 
suitable monomers which can be employed therein. This restriction results 
from the use of a first segment precursor which generally contains two 
different terminal functional groups, each of which is capable of 
reaction. Since it is desired therein to react only one of these groups, 
the selection of monomers meeting this condition is limited. Additionally, 
the presence of the unreacted terminal polar functional group on the first 
segment diminishes the desired non-polarity of this segment. 
We have now found that by employing a first segment precursor having only 
one reactive functional group per molecule in accordance with the 
teachings of this invention, the aforementioned disadvantages can be 
effectively eliminated, thereby allowing the formation of a more 
distinctly non-polar first segment and the use of other preferred monomers 
such as isocyanates (both in stabilizer and particle formation) which 
advantageously offer more rapid, complete reactions and simpler process 
conditions. 
Best Mode of the Invention 
The polymeric dispersion stabilizer of the invention, as described above, 
is characterized in comprising a first segment being formed from a long 
chain hydrocarbon molecule having only one reactive group present on the 
molecule. This hydrocarbon molecule generally has a number average 
molecular weight (M .sub.n) in the range of beteen about 350 and about 
3300, preferably between about 1500 and about 2500. Included among such 
molecules, i.e., first segment precursors, are capped condensation 
polymers. The capped condensation polymer are obtained from uncapped 
polymers. Such uncapped polymers may be made, for example, by condensation 
reactions producing a polyester or polyether. The most convenient monomers 
to use are hydroxy acids or lactones. The hydroxy acids self-condense to 
form hydroxy acid polymers. In such cases, wherein the resultant polymer 
contains e.g., two different reactive groups per molecule, the polymers 
are subsequently capped, i.e., one of the two functional groups is reacted 
(blocked) so as to leave only one reactive group on the polymer. For 
example, a hydroxy fatty acid such as 12-hydroxystearic acid may be 
self-condensed to form poly (12-hydroxystearic acid), which is then capped 
by reaction with e.g., an alkyl monocarboxylic acid. In this embodiment, 
the carboxyl group of the monocarboxylic acid reacts with the hydroxyl 
group of the poly (acid) leaving only one reactive group, the carboxyl 
group, on the polymer. These reactions, the self-condensation and capping, 
may be carried out in situ with singularly combined materials or in two 
steps as would be apparent to one skilled in the art. 
Somewhat more complex, but still useful polyesters may be made by reacting 
diacids with diols. For example, 1,12-dodecanediol may be reacted with 
sebacic acid or its diacid chloride to form a component which could then 
be capped and employed as described above as the first segment precursor. 
As would be apparent to one skilled in the art, a variety of caping 
materials may be employed in the subject invention, whose selection would 
be dependent on the particular functional group to be capped. In the 
embodiment wherein poly (12-hydroxystearic acid) is employed and it is 
desired to react (cap) the terminal hydroxyl group, suitable capping 
material would include alkyl monocarboxylic acids and alkyl isocyanates, 
with aliphatic monocarboxylic acids being preferred. In these capping 
materials, the alkyl group preferably comprises C.sub.3 -C.sub.17 carbon 
atoms. 
In order to form the first segment of the stabilizer (alternatively called 
the "macromonomer"), the described first segment precursor (i.e., having 
only one reactive group) is reacted with a monomer containing an ethylenic 
unsaturation, preferably an alpha-beta unsaturation, and having a 
functionality capable of reacting with the reactive group of the first 
segment precursor molecule. Suitable monomers for use with hydroxy or 
carboxyl functional first segment precursors include, for example, those 
having functionality such as isocyanate, glycidyl, hydroxyl or halide (in 
addition to the ethylenic unsaturation). Exemplary and preferred of such 
monomers are acrylic monomers such as isocyoanatoethyl methacrylate, 
glycidyl methacrylates and hydroxy acrylates and methacrylates. In a 
preferred embodiment wherein the first segment precursor comprises blocked 
poly (12-hydroxystearic acid) having only carboxyl group, the monomer 
preferably contains an isocyanate or glycidyl functionality which reacts 
with the carboxyl group of the capped acid to form the desirably non-polar 
first segment of the stabilizer. However, while acrylic monomers, and 
particularly those described above are preferred, any monomer capable of 
reacting with the monofunctional first segment precursor to add an 
ethylenic unsaturation thereto would be useful in this invention as would 
be apparent to one skilled in the art. 
As discussed above, the polymeric dispersion stabilizer of the crosslinked 
dispersions to which 1983. the characterization of the first segment 
precursor of this invention applies are generally those containing at 
least two segments, with the one segment being solvated by the dispersing 
liquid and the other being of different polarity than the first segment 
and relatively insoluble in the dispersing liquid. Various types of such 
polymeric dispersion stabilizers are discussed in the aforementioned 
Makhlouf et al patent, the disclosure of which is hereby incorporated by 
reference. Preferred types of stable crosslinked dispersions to which the 
particular first segment precursor of the stabilizer of this invention 
applies are those in which the dispersion stabilizer is a graft copolymer 
containing two polymeric segments with one segment being solvated by the 
dispersing liquid and the second segment being an anchor polymer of 
different polarity than the first segment and being relatively 
non-solvatable by the dispersing liquid. Such preferred polymeric 
dispersion stabilizers contain pendant groups (e.g., ethylenic 
unsaturation, hydroxyl, etc.) on the anchor polymer which may react with 
the ethylenically unsaturated monomers in the copolymerization process 
used to make the crosslinked dispersed particles. Preferably such chemical 
reaction is by way of addition copolymerization with the ethylenically 
unsaturated monomers used in the preparation of the crosslinked particles 
through ethylenic unsaturation on the anchor segment of the polymeric 
dispersion stabilizer, however such reaction may include that between 
other reactive groups respectively present on the particle monomers and 
anchor polymer. 
The pairs of reactive functionalities present on the ethylenically 
unsaturated monomers reacted to add the ethylenic unsaturation on the 
anchor portion of the dispersion stabilizer graft copolymer can be 
selected from a wide variety of functionalities which will be apparent to 
one skilled in the art. Among the preferred pairs of reactant 
functionalities which may react so as to add ethylenic unsaturation to the 
stabilizer are isocyanate and hydroxyl; acid and epoxide; epoxide and 
amine; acid anhydride and hydroxyl; acid anhydride and amine; acid 
anhydride and mercaptan; hemiformal and amide; carbonate and amine; 
cycloimide and amine; cycloimide and hydroxyl; imine and alkoxysilane, 
etc. 
In addition to such monomers, other monoethylenically unsaturated monomers 
are coreacted therewith to form the anchor polymer of the dispersion 
stabilizer. While it is preferred that these monomers be methacrylic 
monomers, any such monomer containing ethylenic unsaturation could be so 
employed in this invention. Particlarly preferred are alkyl esters of 
acrylic or methacrylic acid having about 1 to about 4 carbons in the alkyl 
group. Suitable examples include propyl acrylate, butyl acrylate, methyl 
methacrylate and ethyl acrylate. Other ethylenically unsaturated monomers 
which may be advantageously employed include, for example, the vinyl 
aromatic hydrocarbons, such as styrene alpha-methyl styrene, vinyl 
toluene, unsaturated esters of organic and inorganic acids, such as vinyl 
acetate, vinyl chloride and the like, and the unsaturated nitriles, such 
as acrylonitrile, methacrylontrile, ethacrylonitrile and the like. 
Generally, the monomers reacted to form the anchor portion of the 
stabilizer include between about 0.5 and about 10.0 weight percent each of 
the monomers employed to add the ethylenic functionality on the anchor 
portion of the stabilizer and between about 99 and about 80.0 weight 
percent of the other monoethylenically unsaturated monomers. 
There are two particularly preferred anchor portions of the dispersion 
stabilizer employed in forming the crosslinked particles to which this 
invention applies (in which the polymeric dispersion stabilizer is of the 
aforementioned, preferred graft copolymerized type) In one, the first 
segment of the stabilizer as taught above is graft copolymerized with 
methyl methacrylate and hydroxyethyl methacrylate, whereafter the 
resulting product containing pendant hydroxyl groups, is reacted with 
isocyanatoethyl methacrylate, thus adding ethylenic unsaturation to the 
stabilizer (by means of the isocyanate-hydroxyl reaction). In another 
embodiment, the first segment of the stabilizer is graft copolymerized 
with methyl methacrylate and glycidyl methacrylate, and thereafter this 
copolymer product, containing pendant epoxy groups, is reacted with 
methacrylic acid to add the ethylenic unsaturation to the stabilizer (by 
means of the acid-epoxide reactions). 
Examplary of one embodiment of the dispersion stabilizer taught herein is 
that made by a multiple-step process which is accomplished in two 
sequential batches. The particles are prepared using the stabilizer in a 
manner which is similar to well known non-aqueous dispersion processing. 
First, 12-hydroxystearic acid is self-condensed to form poly 
(12-hydroxystearic acid), a linear polyester having a terminal carboxyl 
group on one end and a terminal hydroxy group on the other which is 
subsequently capped by reaction with an alkyl monocarboxylic acid, e.g., 
stearic acid. (Alternatively, the capped poly (12-hydroxystearic acid) can 
be prepared in one step by combining all ingredients and allowing them to 
react.) The capped polyacid is then reacted with (1:1 mole ratio) of 
glycidyl methacrylate. The glycidyl functionality reacts with the terminal 
carboxyl functionality to form an ester linkage, a hydroxy group and 
terminal ethylenic unsaturation. This "macromonomer" (0.10 mole) is then 
reacted by free radical polymerization with, for example, methyl 
methacrylate (1.86 moles) and a small amount of hydroxyethyl methacrylate 
(0.169 moles) to form the graft copolymer (stabilizer precursor). This 
graft copolymer is then modified by reacting the hydroxyl group present 
from the polymerized hydroxyethyl methacrylate with isocyanatoethyl 
methacrylate (0.043 moles), thus providing a graft copolymer (stabilizer) 
with vinyl groups or "hooks" extending from the methyl methacrylate 
backbone. 
The monomer solution employed in making the dispersion generally contains 
between about 1 and about 30 weight percent of the stabilizer based on the 
weight of the monomers used to form the particles. 
The crosslinked particles to which the particular stabilizer of this 
invention applies are prepared by addition polymerization of (a) between 
about 0.8 and about 20 weight percent each of first and second 
ethylenically unsaturated monomers, each bearing functionality capable of 
crosslinking reaction with the other and (b) between about 98.4 and about 
60 weight percent of at least one other monoethylenically unsaturated 
monomer. The addition polymerization is carried out in the presence of an 
organic liquid which is a solvent for the polymerizable monomers, but a 
non-solvent for the resultant polymer and on the presence of the 
aforementioned polymeric dispersion stabilizer. 
The crosslinking functionalities on the first and second ethylenically 
unsaturated monomers (a) in this type of particle formation can be 
selected from a wide variety of functionalities which will be apparent to 
those skilled in the art. Among the preferred pairs of crosslinking 
functionalities which may be present on the first and second ethylenically 
unsaturated monomers are: isocyanate and hydroxyl; acid and epoxide; 
epoxide and amine; acid anhydride and mercaptan; hemiformal and amide; 
carbonate and amine; cycloimide and amine; cycloimide and hydroxyl; imine 
and alkoxysilane; etc. 
Optionally, in addition to the first and second monomers or as a 
replacement for a portion of the first andr second monomers employed in 
particle formation, a minor amount of other suitable first and/or second 
monomers from those described above may be employed, as would be apparent 
to one skilled in the art. 
While the first and second ethylenically unsaturated monomers (a) may be 
any ethylenically unsaturated monomer within the scope of such term (i.e., 
any monomer which bears ethylenic unsaturation, including doubly 
unsaturated monomers such as butadiene and which is capable of 
polymerizing in vinyl-type manner) it is preferred that the monomers be 
acrylic monomers (i.e., monomers based on acrylic, methacrylic or 
ethacrylic acids). 
A preferred class of crosslinked polymer particles within the scope of the 
invention is formed by free radical addition copolymerization, in the 
presence of the polymeric dispersion stabilizer and in the presence of a 
hydrocarbon dispersing liquid of: from about 0.8 to about 10, preferably 
from about 1.0 to about 8.0 weight percent of ethylenically unsaturated 
hydroxy monomers, from about 98.2 to about 78, preferably from about 97.5 
to about 82 weight percent of at least one other copolymerizable 
monoethylenically unsaturated monomer and from about 1.0 to about 12, 
preferably from about 1.5 to about 10, weight percent of a crosslinking 
monomer selected from the group consisting of ethylenically unsaturated 
isocyanates. 
The preferred ethylenically unsaturated hydroxy monomers for use in these 
crosslinked dispersions are hydroxy functional acrylates and 
methacrylates, with methacrylates being especially preferred. 
Various other monoethylenically unsaturated monomers may be copolymerized 
with the monomers in the preparation of this class of crosslinked 
dispersion. Although essentially any copolymerizable monoethylenically 
unsaturated monomer may be utilized, depending upon the properties 
desired, the preferred monoethylenically unsaturated monomers are the 
alkyl esters of acrylic or methacrylic acid, particularly those having 
about 1 to about 4 carbons in the alkyl group. Representative of such 
compounds are alkyl acrylates, such as methacrylate, ethyl acrylate, 
propyl acrylate and butyl acrylate and the alkyl methacrylates, such as 
methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl 
methacrylate. Other ethylenically unsaturated monomers which may be 
advantageously employed include, for example, the vinyl aromatic 
hydrcarbons, such as styrene alpha-methyl styrene, vinyl toluene, 
unsaturated esters of organic and inorganic acids, such as vinyl acetate, 
vinyl chloride and the like, and the unsaturated nitriles, such as 
acrylonitrile, methacrylonitrile, ethacrylonitrile and the like. 
Although numerous ethylenically unsaturated isocyanates will come to the 
mind of those skilled in the art, representative of the most preferred 
isocyanate for this class of crosslinked dispersions are monoethylenically 
unsaturated isocyanate monomers such as isocyanatoethyl methacrylate, and 
reaction product of isophorone diisocyanate (IPDI) and hydroxyethyl 
methacrylic acids (1:1 mole ratio). 
In a particularly preferred crosslinked dispersion embodiment within the 
aforementioned class, the monomers used in the addition copolymerization 
to form the dispersed polymer are characterized in that the ethylenically 
unsaturated hydroxy monomer is hydroxyethyl methacrylate, the other 
copolymerizable monoethylenically unsaturated monomer is methyl 
methacrylate and the crosslinking monomer is isocyanatoethyl methacrylate. 
The particles of this invention can be left as dispersions in the solvent 
employed in particle formation or the solvent employed in particle can be 
removed, leaving the particles in a powder form. These particles, when 
present as a dispersion in the solvent or as a dry powder, can be employed 
as flow control agents in liquid system coatings, for example, in such as 
those taught in U.S. application Ser. No. 334,683 to Chattha and Theodore, 
and Nos. 334,685 and 334,799, all filed Dec. 28, 1981. The powdered 
particles formed according to this invention have also been found useful 
as flow control agents in powder coatings. 
Industrial Applicability 
It should be apparent fom the foregoing, that the particles of this 
invention find application in coatings as, for example, flow control 
agents. 
In view of the disclosure, many modifications of this invention will be 
apparent to those skilled in the art. It is intended that all such 
modifications which fall within the true scope of this invention be 
included within the terms of the appended claims. 
The following examples are presented by way of description of the 
composition of the invention and set forth the best mode contemplated by 
the inventors but are not to be construed as limiting.

EXAMPLE 1 
Capped poly (12-hydroxystearic acid): 
12-Hydroxystearic acid (2410.00 g) and xylene (500.00 g) were heated to 
obtain a solution. Tetraisopropyl titanate (1.50 g, Tyzor TPT, DuPont) was 
added to the solution and refluxed for 30 hours under a Dean-Stark water 
separator to collect 106.00 grams water. Fifty grams of stearic acid were 
added to the reaction mixture and refluxing was continued for ten hours 
until no more water was collected. Infrared spectrum of product showed 
complete disappearance of hydroxy absorption band. The molecular weight 
(M.sub.w /M.sub.n) of product was 4195/2110=1.99. 
Macromonomer: 
One gram of Cordova accelerator AMC.sup.TM -2 was added to the above 
solution and heated to 75.degree. C. Glycidyl methacrylate (158.00 g) was 
added dropwise to the solution with contiuous stirring. The reaction 
mixture was stirred at 75.degree. C.-85.degree. C. until almost complete 
disappearance of glycidyl group band. Solids content 71.8%. 
Stabilizer Precursor and Stabilizer: 
The monomers (292.00 g macromonomer, 186.00 g methyl methacrylate and 22.00 
g hydroxyethyl methacrylate) and 5.00 g AIBN in 70.00 g butyl acetate were 
combined and added dropwise to the refluxing butyl acetate (210.00 g) in 
four hours under nitrogen atmosphere. After the addition was complete, 
1.00 g AIBN was added to the reaction mixture and it was refluxed for 2.5 
additional hours. The solids content was 52.80% (precursor). Hydroquinone 
(0.66 g in 10.00 g butyl acetate) was added to the above solution. After 
raising the temperature of reaction mixture to 60.degree. C., 0.25 g 
dibutyltin dilaurate and 6.50 g isocyanatoethyl methacrylate dissolved in 
aliphatic hydrocarbon (40.00 g, b.p. 127.degree.-140.degree. C.) were 
added dropwise. The mixture was stirred at 60.degree. C. until the 
isocyanate group disappeared. Then it was diluted with aliphatic 
hydrocarbon (b.p. 127.degree.-140.degree. C.) to a solids content of 
43.00%. (stabilizer) The molecular weight (M.sub.w /M.sub.n) of this 
product was 10120/4990=2.03. 
Preparation of Non-Aqueous Dispersion: 
In a two-liter flask equipped with a condenser, gas inlet tube, 
thermomenter, sample port and mechanical stirrer was charged 313.00 g 
heptane. As the temperature was raised to the boiling point of heptane, 
methyl methacrylate (13.00 g), stabilizer (3.20 g) and AIBN (1.00 g) were 
poured into the flask. After refluxing the reaction mixture for thirty 
minutes, the following mixture was added dropwise over a period of four 
hours under a nitrogen atmopshere: stabilizer (55.00 g), methyl 
methacrylate (323.00 g), isocyanatoethyl methacrylate (10.00 g), 
hydroxyethyl methacrylate (8.00 g), aliphatic hydrocarbon (135.00 g), 
1-octanethiol (3.50 g) and AIBN (1.40 g). Upon completion of monomer 
addition, 0.40 g AIBN in 5.00 g butyl acetate were added. Refluxing was 
continued for 2.5 additional hours. Solids content was 45.10%, average 
particle size approximately 0.25 .mu.m and viscosity at 25.degree. C. was 
9.3 sec. (Ford Cup #4). 
A coating formulation was prepared by combining the following ingredients: 
______________________________________ 
1. Tetrahydroxy oligomer 28.00 g 
(90% solids, --M.sub.n = 800) 
2. Cymel 325 (80% solids) 10.00 g 
3. Dispersed particles (45.10% solids) 
5.10 g 
4. Phenyl acid phosphate 0.81 g 
(40% in isopropanol) 
5. Methyl amyl ketone 15.00 g 
______________________________________ 
This formulation exhibited no sagging after spraying and during curing at 
130.degree. C. for 20 minutes. The cured film had good physical 
properties. 
EXAMPLE 2 
The preparation of non-aqueous dispersion in Example 1 was repeated with 
the exception in the method of preparing capped poly (12-hydroxystearic 
acid). 12-hydroxystearic acid (2410.00 g), stearic acid (100.00 g) and 
xylene (500.00 g) were heated to obtain a solution. Tetraisopropyl 
titanate (1.50 g, Tyzor TPT) was added to the solution and the mixture was 
refluxed under a Dean-Stark water separator until no more water was 
released. Infrared spectrum of the product showed complete disappearance 
of the hydroxy absorption band. This capped acid was used in preparing a 
non-aqueous dispersion which was combined with the following ingredients 
in preparing a coating formulation: 
______________________________________ 
1. Hydroxy acrylic polymer 32.00 g 
(30% hydroxy monomer, --M.sub.n = 1850 and 
80% solids) 
2. Cymel 325 (80% solids) 13.00 g 
3. Dispersed particles (45.10% solids) 
6.00 g 
4. Phenyl acid phosphate 0.90 g 
(40% in isopropanol) 
5. Methyl amyl ketone 13.00 g 
______________________________________ 
The coating composition exhibited excellent flow control during application 
and baking. In the absence of dispersed particles, the flow control of 
this coating composition was poor. 
EXAMPLE 3 
The stabilizer of Example 1 was employed in preparing particles with lower 
crosslinking density. In a four-liter flask equipped with a condenser, gas 
inlet tube, thermometer, sample port and mechanical stirrer was charged 
630 g heptane. As the temperature was raised to the boiling point of 
heptane, methyl methacrylate (27.00 g), stabilizer (6.50 g) and AIBN (2.00 
g) were poured into the flask. After refluxing the reaction mixture for 
thirty minutes, the following mixture was added dropwise over a period of 
four hours under a nitrogen atmosphere: stabilizer (110.00 g), methyl 
methacrylate (700.00 g), isocyanatoethyl methacrylate (8.00 g), 
hydroxyethyl methacrylate (6.40 g), aliphatic hydrocarbon (270.00 g, b.p. 
127.degree.-140.degree. C.), 1-octanethiol (7.00 g) and AIBN (2.50 g). 
Refluxing was continued for two additional hours. Solids content was 
44.7%, average particle size approximately 0.25 .mu.m and viscosity at 
25.degree. C. was 9.6 sec. (Ford Cup #4). 
Incorporation of this non-aqueous dispersion in high solids coatings 
controls the flow but the control is slightly inferior to that obtained 
from the dispersed particles of Example 1. 
EXAMPLE 4 
Example 1 is repeated by using the same stabilizer but different amount of 
ingredients for preparing the dispersion. In a one-liter flask equipped 
with a condenser, gas inlet tube, thermometer, sample port and mechanical 
stirrer was charged 157.00 g heptane. To the boiling heptane was added a 
mixture of methyl methacrylate (7.00 g), stabilizer (1.60 g) and AIBN 
(0.50 g). After refluxing the reaction mixture for thirty minutes, the 
following mixture was added over a period of three hours under a nitrogen 
atmosphere: stabilizer (27.50 g), methyl methacrylate (100.00 g), styrene 
(65.00 g), isocyanatoethyl methacrylate (10.00 g), hydroxyethyl 
methacrylate (8.00 g), 60.00 g aliphatic hydrocarbon (b.p. 
127.degree.-140.degree. C.), 1-octanethiol (1.75 g) and AIBN (0.70 g). 
Upon completion of monomer addition, 0.2 g AIBN in 5.00 g butyl acetate 
were added. Refluxing was continued for three additional hours. Solids 
content was 44.60%, average particle size 0.34 .mu.m and viscosity at 
25.degree. C. was 10.8 sec. (Ford Cup #4). Addition of these dispersed 
particles in a high solids coating composition resulted in a paint with 
good flow properties. 
EXAMPLE 5 
Example 1 was repeated with the exception that the following amounts of 
ingredients were used for the preparation of dispersion: To 197.00 g 
heptane was added a mixture of methyl methacrylate (7.00 g), stabilizer 
(1.60 g) and AIBN (0.60 g). After refluxing the reaction mixture for 
thirty minutes, the following mixture was added over a period of three 
hours under a nitrogen atmosphere: stabilizer (27.50 g), methyl 
methacrylate (161.00 g) isocyanatoethyl methacrylate (23.00 g), 
hydroxyethyl methacrylate (18.50 g), aliphatic hydrocarbon (120.00 g), 
1-octanethiol (1.75 g) and AIBN (0.80 g). The mixture was refluxed for 
thirty minutes. The dispersed particles were used in preparing coating 
compositions. 
EXAMPLE 6 
Example 4 was repeated with the exception that the macromonomer was 
prepared by the following procedure: capped poly (12-hydroxystearic acid) 
(500.00 g), isocyanatoethyl methacrylate (45.00 g), dibutylin dilaureate 
(0.23 g) and hydroquinone (1.50 g) were heated at 60.degree. C. with 
stirring until all the isocyanate groups disappeared. This macromonomer 
was employed in preparing the stabilizer as in Example 4. Dispersed 
particles resulting from this stabilizer were suitable for controlling the 
flow of high solids coatings based on acrylic hydroxy copolymers. 
EXAMPLE 7 
Example 1 was repeated with the exception that the stabilizer precursor was 
employed in stabilizing the particles during dispersion polymerization. 
The dispersed particles had an average particle size of 0.32 .mu.m and 
viscosity at 25.degree. C. of 9.9 sec. (Ford Cup #4). When these 
dispersions were added to coating compositions, they controlled the flow 
during film formation and baking. 
EXAMPLE 8 
Example 1 was repeated with the single exception that the amount of 
stabilizer used for preparing the non-aqueous dispersion was lowered to 
20.00 g. The dispersed particles were combined with other ingredients to 
prepare coatings with improved flow properties. 
EXAMPLE 9 
The procedure of Example 4 was repeated with the single exception that 
40.00 g stabilizer were employed in preparing the non-aqueous dispersion. 
Solids content was 45.00%, average particle size 0.22 .mu.m and viscosity 
at 25.degree. C. was 9.5 sec. (Ford Cup #4). The dispersed particles were 
suitable for controlling the flow of high solids coatings. 
EXAMPLE 10 
The procedure of preparing the stabilizer in Example 1 was repeated but the 
reactive monomers in preparing the cross-linked particles were changed. In 
a two-liter flask equipped with a condenser, gas inlet tube, thermometer, 
sample port and mechanical stirrer were charged 320.00 g heptane. As the 
temperature was raised to the boiling point of heptane, methyl 
methacrylate (13.00 g), stabilizer (3.20 g, Example 1) and AIBN (1.00 g) 
were poured into the flask. After refluxing the reaction mixture for 
thirty minutes, the following mixture was added dropwise over a period of 
three hours under a nitrogen atmosphere: stabilizer (Example 1, 55.00 g), 
methyl methacrylate (223.00 g), styrene (100.00 g), glycidyl methacrylate 
(18.00 g), methacrylic acid (11.00 g), 1-octanethiol (3.50 g), 130.00 
aliphatic hydrocarbon (b.p. 127.degree.-140.degree. C.), dimethyldodecyl 
amine (0.90 g) and AIBN (1.40 g). Upon completion of monomer addition, 
0.5g AIBN in 4.00g butyl acetate were added. Refluxing was continued for 
one hour. Solids content was 47.30 %, average particle size 0.31 .mu.m and 
viscosity at 25.degree. C. was 10 sec. (Ford Cup #4). The crosslinked, 
dispersed particles were suitable for controlling the flow of coatings 
prepared by mixing the following ingredients: T1 1. Tetrahydroxy 
oligomer 70.0 g (90% solids, M.sub.n = 800) 2. Cymel 325 (80% solids) 
22.50 g 3. Dispersed particles (47.30% solids) 12.50 g 4. Phenyl acid 
phosphate 2.00 g (40% in isopropanol) 5. Methyl amyl ketone 35.00 g? 
This formulation was applied on primed panels and exhibited no sagging 
during film formation and baking at 130.degree. C. for 20 minutes. The 
cured films exhibited excellent properties. 
EXAMPLE 11 
Example 10 was repeated with the single exception that the dispersion was 
prepared by reducing the amounts of crosslinking monomers (glycidyl 
methacrylate (9.00 g) and methacrylic acid (5.50 g). All other ingredients 
remained the same as in Example 10. The solids content of dispersion was 
47.00%, average particle size 0.23 .mu.m and viscosity of 25.degree. C. 
was 9.8 sec. (Ford Cup #4). The dispersed particles controlled the flow of 
coatings. 
EXAMPLE 12 
Example 10 was repeated with the single exception that the amount of 
glycidyl methacrylate (38.00 g) and methacrylic acid (23.00 g) were 
increased but all other ingredients were maintained at same level as in 
Example 10. The solids content was 45.60% and average particle size 0.34 
.mu.m. 
EXAMPLE 13 
Example 10 was repeated with the exception that the stabilizer precursor 
was employed in preparing the dispersion. The dispersed particles 
controlled the flow of coatings during film formation and baking but the 
control is slightly inferior to that obtained from the particles of 
Example 10. 
EXAMPLE 14 
The stabilizer of Example 1 was employed in preparing this dispersion. In a 
one-liter flask equipped with condenser, gas inlet tube, thermometer, 
sample port and mechanical stirrer was charged 165.00 g heptane. To the 
boiling heptane was added a mixture of methyl methacrylate (7.00 g), 
stabilizer (1.60 g, Example 1) and AIBN (0.50 g). The reaction mixture was 
refluxed for thirty minutes and a mixture of ingredients was added over a 
period of three hours under a nitrogen atmosphere: stabilizer (32.00 g), 
methyl methacrylate (117.00 g), glycidyl methacrylate (32.00 g), 
methacrylic acid (30.00 g), 1-octanethiol (1.75 g), aliphatic hydrocarbon 
(20 g, b.p. 127.degree.-140.degree. C.) and AIBN (0.70 g). Refluxing was 
continued for two additional hours. The dispersed particles exhibit very 
soft settling. 
EXAMPLE 15 
Example 1 was repeated with the exception that the stabilizer precursor was 
employed in preparation of dispersion. The dispersed particles controlled 
the flow of coatings during film formation and baking.