This invention relates to polymers which comprise the reaction product of: PA1 (A) about 1-99.8 weight percent of one or more nonionic, cationic, anionic or amphoteric monomers; PA1 (B) about 0-98.8 weight percent of one or more monoethylenically unsaturated monomers different from (A); PA1 (C) about 0.1-98.8 weight percent of one or more monoethylenically unsaturated macromonomers different from (A) and (B); PA1 (D) about 0.1-98.8 weight percent of one or more monoethylenically unsaturated macromonomers different from (A), (B) and (C); PA1 (E) about 0-20 weight percent or greater of one or more polyethylenically unsaturated monomers different from (A), (B), (C) and (D); and PA1 (F) about 0-25 weight percent or greater of one or more acrylates and/or methacrylates derived from a strong acid or a salt of a strong acid different from components (A), (B), (C), (D) and (E). The polymers of this invention are especially useful as thickeners and dispersants for aqueous systems, especially latex paints.

RELATED APPLICATIONS 
The following are related, commonly assigned applications, filed on an even 
date herewith: U.S. patent application Ser. No. 08/395,720, copending, and 
U.S. patent application Ser. No. 08/395,440, copending, both of which are 
incorporated herein by reference. 
BRIEF SUMMARY OF THE INVENTION 
Technical Field 
This invention relates to polymers which contain macromonomer mixtures and 
which can contain nonionic, cationic, anionic and/or amphoteric monomers, 
and to dispersions and coating compositions containing said polymers. The 
polymers of this invention are especially useful as thickeners and 
dispersants for aqueous systems, especially latex paints. 
Background of the Invention 
Thickeners for aqueous systems are needed for various purposes, such as for 
architectural coatings, industrial coatings, automotive coatings and the 
like to improve rheology of the coatings. Also, any industry using 
pigments, fillers, or other solids needs to stabilize the system from the 
time of manufacture to the time of use. Because solid particles have 
densities that are larger than that of the liquid medium in which they are 
suspended, they tend to settle due to gravity. Dispersants provide the 
desired stability. 
The typical waterborne latex paint contains pigment (often titanium 
dioxide), latex, clay extenders, pigment dispersants, colorants, rheology 
modifiers (thickeners), anti-foam agent, coalescent, metal oxides (such as 
zinc oxide), and fungicide. Without dispersants and thickeners, a 
satisfactory waterborne latex paint could not be made. There is a 
continuing need for dispersants and thickeners that provide desired latex 
paint stability and rheology without negatively influencing other latex 
paint properties such as in-can viscosity stability, color acceptance, 
colorant float, and film properties of the paint: wet and dry film 
opacity, adhesion to various substrates, film gloss, and the water and 
alkali-resistance of the dry film. 
Disclosure of the Invention 
This invention relates in part to polymers comprising the reaction product 
of: 
(A) about 1-99.8, preferably about 10-70, weight percent of one or more 
nonionic, cationic, anionic and/or amphoteric monomers; 
(B) about 0-98.8, preferably about 30-85, weight percent of one or more 
monoethylenically unsaturated monomers, typically ethyl acrylate, 
different from component (A); 
(C) about 0.1-98.8, preferably about 5-60, weight percent of one or more 
monoethylenically unsaturated macromonomers different from components (A) 
and (B); 
(D) about 0.1-98.8, preferably about 5-60, weight percent of one or more 
monoethylenically unsaturated macromonomers different from components (A), 
(B) and (C); 
(E) about 0-20, preferably about 0-10, weight percent or greater of one or 
more polyethylenically unsaturated monomers, typically trimethylol propane 
triacrylate, different from components (A), (B), (C) and (D); and 
(F) about 0-25, preferably about 0.1-25, weight percent or greater of one 
or more acrylates and/or methacrylates derived from a strong acid or a 
salt of a strong acid, typically 2-sulfoethyl methacrylate, different from 
components (A), (B), (C), (D) and (E). For purposes of this invention, the 
above-identified polymer is considered a dispersant when the molecular 
weight is less than about 50,000 and a thickener when the molecular weight 
is greater than about 50,000. However, it is appreciated that some 
dispersants cause thickening and some thickeners cause dispersing of 
particles. 
This invention also relates in part to an emulsion of the above-identified 
polymer in water, which emulsion is useful as a thickening or dispersing 
agent in aqueous compositions. In order to obtain the thickening effect, 
the thickener is dissolved in the aqueous composition to be thickened. In 
order to obtain the dispersing effect, the dispersant is dissolved in the 
aqueous composition containing particles. 
This invention further relates in part to an aqueous composition, and more 
particularly an improved latex paint composition containing the 
above-defined polymer. 
This invention yet further relates in part to a process for thickening an 
aqueous composition which comprises adding the above-defined thickener to 
an aqueous composition and dissolving the thickener in the aqueous 
composition. 
This invention also relates in part to a process for dispersing an aqueous 
coating composition containing particles which comprises adding the 
above-defined dispersant to said aqueous coating composition and 
dissolving the dispersant therein. 
Detailed Description 
Illustrative nonionic, cationic, anionic and amphoteric monomers useful in 
this invention include those monomers which impart water solubility to the 
polymer. Preferably, a large proportion of component (A) is employed to 
impart water solubility to the polymers of this invention. The key to 
water solubility lies in positioning sufficient numbers of hydrophilic 
functional groups along the backbone or side chains. Suitable functional 
groups which impart water solubility and suitable nonionic, cationic, 
anionic and amphoteric monomers useful in this invention are described in 
Water-Soluble Polymers, Synthesis, Solution Properties and Applications, 
ACS Symposium Series 467, American Chemical Society (1991), which is 
incorporated herein by reference. Mixtures of nonionic, cationic, anionic 
and amphoteric monomers may be employed in this invention, e.g., mixtures 
of nonionic monomers, mixtures of nonionic and cationic monomers, etc. 
Illustrative nonionic monomers useful in this invention include, for 
example, acrylamide, N, N-dimethyl acrylamide, vinyl pyrrolidone, ethylene 
oxide, vinyl alcohol, vinyl acetate, N-vinylpyrrolidinone, hydroxyethyl 
acrylate, phosphate-containing monomers and the like including mixtures 
thereof. Illustrative cationic monomers useful in this invention include, 
for example, ammonium, sulfonium and phosphonium salts, preferably 
quarternary ammonium salts such as diallyldimethylammonium chloride, 
diallyldiethylammonium chloride, diethylaminoethyl methacrylate, 
dimethylaminoethyl methacrylate, methacryloyloxyethyltrimethylammonium 
sulfate, methacryloyloxyethyltrimethylammonium chloride, 
3-(methacrylamido)propyltrimethylammonium chloride and the like including 
mixtures thereof. 
Illustrative anionic monomers useful in this invention include, for 
example, acrylic acid, methacrylic acid, maleic anhydride, p-styrene 
carboxylic acids, p-styrene sulfonic acids, vinyl sulfonic acid, 
2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, 3-sulfopropyl 
acrylate, 2-acrylamido-2-methylpropane sulfonic acid, 
3-acrylamido-3-methylbutanoic acid, vinyl phosphonic acid, other 
phosphate-containing monomers and the like including mixtures thereof and 
salts thereof. Illustrative amphoteric monomers useful in this invention 
contain zwitterions on the same monomers, i.e., betaines, or along the 
same polymer backbone, i.e., ampholytes, and include, for example, 
N,N-dimethyl-N-methacryloxyethyl-N-(3-sulfopropyl) ammonium-betain, 
N,N-dimethyl-N-methacryl-amidopropyl-N-(3-sulfopropyl)ammonium-betain, 
1-(3-sulfopropyl)-2-vinylpyridinium-betain, 
3-(2-acrylamido-2-methyl-propyldimethylammonio)-1-propanesulfonate, 
N-vinylpyrrolidone-co-N,N-dimethyl-N-methacroyloxyethylammoniopropanesulfo 
nate, 
N-vinyl-pyrrolidone-co-N,N-dimethyl-N-methacroylamidopropylammoniopropanes 
ulfonate, N-vinylpyrrolidone-co-2-vinylpyridiniopropanesulfonate and the 
like including mixtures thereof. 
Preferably, a large proportion of one or more alpha, betamonoethylenically 
unsaturated carboxylic acid monomers can be present in the polymers of 
this invention. Various carboxylic acid monomers can be used, such as 
acrylic acid, methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid, 
crotonic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic 
acid, maleic acid and the like including mixtures thereof. Methacrylic 
acid is preferred. A large proportion of carboxylic acid monomer is 
essential to provide a polymeric structure which will solubilize and 
provide a thickener when reacted with an alkali like sodium hydroxide. 
The polymers of this invention can also contain a significant proportion of 
one or more monoethylenically unsaturated monomers (i.e., component (B)). 
The preferred monomers provide water insoluble polymers when 
homopolymerized and are illustrated by acrylate and methacrylate esters, 
such as ethyl acrylate, butyl acrylate or the corresponding methacrylate. 
Other monomers which can be used are styrene, alkyl styrenes, vinyl 
toluene, vinyl acetate, vinyl alcohol, acrylonitrile, vinylidene chloride, 
vinyl ketones and the like. Nonreactive monomers are preferred, those 
being monomers in which the single ethylenic group is the only group 
reactive under the conditions of polymerization. However, monomers which 
include groups reactive under baking conditions or with divalent metal 
ions such as zinc oxide may be used in some situations, like hydroxyethyl 
acrylate. 
Other illustrative monoethylenically unsaturated monomers useful in this 
invention include, for example, propyl methacrylate, isopropyl 
methacrylate, butyl methacrylate, n-amyl methacrylate, sec-amyl 
methacrylate, hexyl methacrylate, lauryl methacrylate, stearyl 
methacrylate, ethyl hexyl methacrylate, crotyl methacrylate, cinnamyl 
methacrylate, oleyl methacrylate, ricinoleyl methacrylate, hydroxy ethyl 
methacrylate, hydroxy propyl methacrylate, vinyl propionate, vinyl 
butyrate, vinyl tert-butyrate, vinyl caprate, vinyl stearate, vinyl 
laurate, vinyl oleate, vinyl methyl ether, vinyl ethyl ether, vinyl 
n-propyl ether, vinyl iso-propyl ether, vinyl n-butyl ether, vinyl 
iso-butyl ether, vinyl iso-octyl ether, vinyl phenyl ether, a-chlorovinyl 
phenyl ether, vinyl/-naphthyl ether, methacryonitrile, acrylamide, 
methacrylamide, N-alkyl acrylamides, N-aryl acrylamides, N-vinyl 
pyrrolidone, N-vinyl-3morpholinones, N-vinyl-oxazolidone, 
N-vinyl-imidazole and the like including mixtures thereof. 
The macromonomers useful in this invention (i.e., component (C)) can be 
represented by the formula: 
##STR1## 
wherein: R.sup.1 is a monovalent residue of a substituted or unsubstituted 
complex hydrophobe compound; 
each R.sup.2 is the same or different and is a substituted or unsubstituted 
divalent hydrocarbon residue; 
R.sup.3 is a substituted or unsubstituted divalent hydrocarbon residue; 
R.sup.4, R.sup.5 and R.sup.6 are the same or different and are hydrogen or 
a substituted or unsubstituted monovalent hydrocarbon residue; and 
z is a value of 0 or greater. 
The macromonomers useful in this invention (i.e., component (D)) can be 
represented by the formula: 
##STR2## 
wherein: R.sup.1' is a monovalent residue of a substituted or 
unsubstituted hydrophobe compound other than a complex hydrophobe 
compound; 
each R.sup.2' is the same or different and is a substituted or 
unsubstituted divalent hydrocarbon residue; 
R.sup.3' is a substituted or unsubstituted divalent hydrocarbon residue; 
R.sup.4', R.sup.5' and R.sup.6' are the same or different and are 
hydrogen or a substituted or unsubstituted monovalent hydrocarbon residue; 
and 
z' is a value of 0 or greater. 
The macromonomers useful in this invention can be represented by the 
formulae (I) and (II) above. The macromonomer compounds useful in this 
invention can be prepared by a number of processes, such as described in 
U.S. Pat. Nos. 5,292,843, 5,292,828 and U.S. Pat. No. Reissue 33,156, all 
incorporated herein by reference. 
Illustrative substituted and unsubstituted divalent hydrocarbon residues 
represented by R.sup.2 in formula (I) and R.sup.2' in formula (II) above 
include those described for the same type of substituents in formulae 
(III) and (IV) below. Illustrative substituted and unsubstituted 
monovalent hydrocarbon residues represented by R.sup.4, R.sup.5 and 
R.sup.6 in formula (I) and by R.sup.4', R.sup.5' and R.sup.6' in formula 
(II) above include those described for the same type of substituents in 
formulae (III) and (IV) below. 
Illustrative substituents represented by R.sup.3 in formula (I) and 
R.sup.3' in formula (II) above include, for example, the organic residue 
of ethers, esters, urethanes, amides, ureas, urethanes, anhydrides and the 
like including mixtures thereof. The substituents represented by R.sup.3 
in formula (I) and R.sup.3' in formula (II) above can be generally 
described as a "linkage" between the complex hydrophobe bearing surfactant 
or alcohol, and the unsaturation portion of the macromonomer compound. 
Preferred linkages include the following: urethane linkages from the 
reaction of an isocyanate with a nonionic surfactant; urea linkages from 
the reaction of an isocyanate with an amine bearing surfactant; 
unsaturated esters of surfactants such as the esterification product of a 
surfactant with of an unsaturated carboxylic acid or an unsaturated 
anhydride; unsaturated esters of alcohols; esters of ethyl acrylate 
oligomers, acrylic acid oligomers, and allyl containing oligomers; half 
esters of surfactants such as those made by the reaction of a surfactant 
with maleic anhydride; unsaturated ethers prepared by reacting vinyl 
benzyl chloride and a surfactant or by reacting an allyl glycidyl ether 
with a surfactant, alcohol, or carboxylic acid. 
The oxyalkylene moieties included in the macromonomer compounds of formulae 
(I) and (II) may be homopolymers or block or random copolymers of straight 
or branched alkylene oxides. Mixtures of alkylene oxides such as ethylene 
oxide and propylene oxide may be employed. It is understood that each 
R.sup.2 group in formula (I) or R.sup.2' group in formula (II) in a 
particular substituent for all positive values of z and z' can be the same 
or different. 
Illustrative monovalent residues of substituted and unsubstituted complex 
hydrophobe compounds represented by R.sup.1 in formula (I) include, for 
example, those derived from substituted and unsubstituted complex 
hydrophobe compounds represented by the formula: 
##STR3## 
wherein R.sub.1 and R.sub.2 are the same or different and are hydrogen or 
a substituted or unsubstituted monovalent hydrocarbon residue, R.sub.3 is 
a substituted or unsubstituted divalent or trivalent hydrocarbon residue, 
each R.sub.4 is the same or different and is a substituted or 
unsubstituted divalent hydrocarbon residue, each R.sub.5 is the same or 
different and is a substituted or unsubstituted divalent hydrocarbon 
residue, R.sub.6 is hydrogen, a substituted or unsubstituted monovalent 
hydrocarbon residue or an ionic substituent, a and b are the same or 
different and are a value of 0 or 1, and x and y are the same or different 
and are a value of 0 or greater; provided at least two of R.sub.1, 
R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are a hydrocarbon residue 
having greater than 2 carbon atoms in the case of R.sub.1, R.sub.2 and 
R.sub.6 or having greater than 2 pendant carbon atoms in the case of 
R.sub.3, R.sub.4 and R.sub.5. 
Other monovalent residues of substituted and unsubstituted complex 
hydrophobe compounds represented by R.sup.1 in formula (I) include, for 
example, those derived from substituted and unsubstituted complex 
hydrophobe compounds represented by the formula: 
##STR4## 
wherein R.sub.7 and R.sub.8 are the same or different and are hydrogen or 
a substituted or unsubstituted monovalent hydrocarbon residue, R.sub.11 
and R.sub.14 are the same or different and are hydrogen, a substituted or 
unsubstituted monovalent hydrocarbon residue or an ionic substituent, 
R.sub.9 and R.sub.12 are the same or different and are a substituted or 
unsubstituted divalent or trivalent hydrocarbon residue, each R.sub.10 is 
the same or different and is a substituted or unsubstituted divalent 
hydrocarbon residue, each R.sub.13 is the same or different and is a 
substituted or unsubstituted divalent hydrocarbon residue, R.sub.15 is a 
substituted or unsubstituted divalent hydrocarbon residue, d and e are the 
same or different and are a value of 0 or 1, and f and g are the same or 
different and are a value of 0 or greater; provided at least two of 
R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, 
R.sub.14 and R.sub.15 are a hydrocarbon residue having greater than 2 
carbon atoms in the case of R.sub.7, R.sub.8, R.sub.11 and R.sub.14 or 
having greater than 2 pendant carbon atoms in the case of R.sub.9, 
R.sub.10, R.sub.12, R.sub.13 and R.sub.15. 
Such monovalent residues of substituted and unsubstituted complex 
hydrophobe compounds represented by formulae (III) and (IV) and processes 
for the preparation of complex hydrophobes are described in U.S. Pat. Nos. 
5,292,843 and 5,292,828. 
Illustrative monovalent residues of substituted and unsubstituted 
hydrophobe compounds represented by R.sup.1' in formula (II) include, for 
example, alkyl radicals including linear or branched primary, secondary or 
tertiary alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, amyl, 
sec-amyl, t-amyl, 2-ethylhexyl and the like; aryl radicals such as phenyl, 
naphthyl and the like; arylalkyl radicals such as benzyl, phenylethyl, 
tri-phenylmethylethane and the like; alkylaryl radicals such as 
octylphenyl, nonylphenyl, dodecylphenyl, tolyl, xylyl and the like; and 
cycloalkyl radicals such as cyclopentyl, cyclohexyl, cyclohexylethyl and 
the like. 
Preferred macromonomer compounds useful in this invention include those 
represented by the formula: 
##STR5## 
wherein R.sup.1, R.sup.2 and z are as defined herein. Other preferred 
macromonomer compounds useful in this invention include those represented 
by formula (V) in which R.sup.1 is R.sup.1', R.sup.2 is R.sup.2' and z is 
z'. 
The polymers of this invention may further be modified by introducing an 
amount of component (E), namely, one or more polyethylenically unsaturated 
copolymerizable monomers effective for crosslinking, such as 
diallylphthalate, divinylbenzene, allyl methacrylate, trimethylol propane 
triacrylate, ethyleneglycol diacrylate or dimethacrylate, 1,6-hexanediol 
diacrylate or dimethylacrylate, diallyl benzene, and the like. Thus, from 
about 0.05 or less to about 20% or greater of such polyethylenically 
unsaturated compound based on total weight of monomer may be included in 
the composition forming the polymer. The resulting polymers are either 
highly branched or in the form of three-dimensional networks. In the 
neutralized salt form, those networks swell in an aqueous system to act as 
a highly efficient thickener. 
Other illustrative polyethylenically unsaturated monomers useful in this 
invention include, for example, any copolymerizable compound which 
contains two or more nonconjugated points of ethylenic unsaturation or two 
or more nonconjugated vinylidene groups of the structure, CH.sub.2 
.dbd.C.dbd., such as divinyltoluene, trivinylbenzene, divinylnaphthalene, 
trimethylene glycol diacrylate or dimethacrylate, 
2-ethylhexane-1,3-dimethyacrylate, divinylxylene, divinylethylbenzene, 
divinyl ether, divinyl sulfone, allyl ethers of polyhdric compounds such 
as of glycerol, pentaerythritol, sorbitol, sucrose and resorcinol, 
divinylketone, divinylsulfide, allyl acrylate, diallyl maleate, diallyl 
fumarate, diallyl phthalate, diallyl succinate, diallyl carbonate, diallyl 
malonate, diallyl oxalate, diallyl adipate, diallyl sebacate, diallyl 
tartrate, diallyl silicate, triallyl tricarballylate, triallyl aconitate, 
triallyl citrate, triallyl phosphate, N,N-methylenediacrylamide, 
N,N'-methylenedimethacrylamide, N,N'-ethylidenediacrylamide and 
1,2-di-(a-methylmethylenesulfonamide)-ethylene. 
The polymers of this invention also may include an amount of component (F), 
namely one or more acrylates and/or methacrylates derived from a strong 
acid or a salt of a strong acid. As used herein, "strong acid(s)" shall 
mean those acids substantially dissociated at a pH of 2 and shall include, 
for example, sulfonic acid and the like. Illustrative acrylates and 
methacrylates derived from a strong acid or a salt of a strong acid 
include, for example, 2-sulfoethyl methacrylate, 3-sulfopropyl 
methacrylate, 3-sulfopropyl acrylate, and the like. Other acrylates and 
methacrylates derived from a strong acid or a salt of a strong acid 
include those disclosed in U.S. Pat. No. 3,024,221. Suitable salts 
include, for example, the sodium, potassium, ammonium, etc., salt of the 
strong acid. The acrylates and methacrylates derived from a strong acid or 
a salt of a strong acid are employed in the emulsion polymerization 
process in an amount sufficient to reduce plating and/or grit formation 
during said process, preferably from about 0.1 to about 25 weight percent, 
more preferably from about 0.1 to about 10 weight percent, and most 
preferably from about 0.1 to about 2.0 weight percent. 
The use of acrylates and/or methacrylates derived from a strong acid or a 
salt of a strong acid in a process for preparing an aqueous polymer 
emulsion useful as a dispersing or thickening agent in aqueous 
compositions significantly reduces both waste polymer ("scrap") in the 
form of reactor residue ("plating") and the formation of large particle 
size suspended aggregates ("grit") in the aqueous polymer emulsion 
products. Such plating and grit can jeopardize the commercial and economic 
viability of a process or product. Illustrative acrylates and/or 
methacrylates derived from a strong acid or a salt of a strong acid useful 
in this invention and processes for preparation thereof are disclosed in 
copending U.S. Pat. No. 5,399,618, which is incorporated herein by 
reference. 
Factors that influence the performance of the dispersants and thickeners of 
this invention include chemical composition (the concentration of 
carboxyl, sulphonic, or phosphate moieties, hydrophobicity and glass 
transition temperature of the polymer through the use of comohomers, such 
as acrylates, methacrylates, styrene, isobutylene, vinyl esters, and 
acrylamide), molecular weight and polydispersity, the choice of 
neutralizing agent (i.e., the dispersants' counter-ion), and dosage. 
Optionally, the dispersants and thickeners can be further modified through 
the use of monomers or post treatments or reactions to facilitate latent 
cross-linking, air-cure, ambient cure, or thermosetting properties. 
Although any effective amount of the polymeric dispersant and thickener may 
be employed for dissolution, typically from about 0.01 to about 20%, 
preferably from about 0.01 to about 5%, and most preferably from about 0.1 
to about 3% by weight, based on the weight of the final aqueous 
composition including dispersant and thickener is used. For latex paint 
compositions, the dispersant or thickener may be dissolved therein in an 
amount of from about 0.01 to about 5%, and preferably from about 0.1 to 
about 3% by weight, based on the weight of the total composition including 
polymeric dispersant and thickener. 
The particles of the composition of this invention can be organic or 
inorganic or hydrophilic or hydrophobic. This invention is particularly 
useful for dispersing titanium dioxide in a latex paint composition. 
However, it is appreciated that the dispersants of this invention also 
have applicability for dispersing other normally charged particles, such 
as precipitated and ground calcium carbonate, silica, aluminum hydrate, 
kaolin clay, composite pigments, gypsum, synthetic organic pigments which 
have anionic components on their surface, e.g., polystyrene spheres, 
colorants, and mixture of the above. This invention is not intended to be 
limited in any manner by permissible particles which may be dispersed 
using the dispersants of this invention. 
The polymers of this invention can be prepared via a variety of 
polymerization techniques known to those skilled in the art, provided such 
polymerization techniques impart (i) colloidal stabilization to the 
polymer particles and (ii) a medium wherein electrostatic interaction of 
the polymer particles can take place. The technique of polymerization 
influences the microstructure, monomer sequence distribution in the 
polymer backbone and its molecular weight to influence the performance of 
the polymer. Illustrative polymerization techniques include, for example, 
conventional and staged aqueous emulsion polymerization via batch, 
semi-continuous, or continuous processes, miniemulsion and microemulsion 
polymerization, aqueous dispersion polymerization, interfacial 
polymerization, aqueous suspension polymerization, and the like. 
For purposes of this invention, the terms "aqueous emulsion", "aqueous 
emulsion polymerization", and like terms, are contemplated to include all 
those polymerizations which provide (i) colloidal stabilization of the 
polymer particles and (ii) a medium wherein electrostatic interaction of 
the polymer particles can take place. As used herein, the term "aqueous 
polymer emulsions", and like terms, are contemplated to include all those 
polymer products prepared by aqueous emulsion or aqueous emulsion 
polymerization. 
The polymerization system may contain amounts (0.01 to 5% by weight, based 
on monomer weight) of the chain transfer agent mercaptans such as 
hydroxyethyl mercaptan, .beta.-mercaptopropionic acid and alkyl mercaptans 
containing from about 4 to 22 carbon atoms, e.g., ethyl hexyl mercapto 
propionate and tertiary dodecyl mercaptan, and the like. The use of 
mercaptan modifier reduces the molecular weight of the polymeric 
dispersant and therefore improves its dispersing efficiency. 
In an embodiment of this invention, the emulsion polymerization is carried 
out in the presence of one or more buffers. Illustrative buffers useful in 
this invention include, for example, sodium acetate, sodium bicarbonate, 
potassium carbonate and the like. The buffers are employed in the emulsion 
polymerization process in an amount sufficient to reduce plating and/or 
grit formation during said process, preferably from about 0.01 to about 
1.0 weight percent, more preferably from about 0.1 to about 0.5 weight 
percent. 
The order of addition of the dispersant in the pigment dispersion process 
is important to put the most suitable dispersant on the pigment first to 
promote color development when the stabilized pigment is subsequently used 
in the paint system. 
The thickeners of this invention possess structural attributes of two 
entirely different types of thickeners (those which thicken by pH 
dependent solubilization, e.g., alkali solubilization, of a high molecular 
weight entity, and those which thicken due to association), and this may 
account for the superior thickener properties which are obtained herein. 
An enhancement of thickening (herein termed "co-thickening") can result 
upon the addition of a surfactant to an aqueous system containing the 
thickener of this invention, when the thickener is solubilized. Such 
co-thickening is described, for example, in U.S. Pat. Nos. 5,292,843 and 
5,292,828. An enhancement of dispersing (herein termed "co-dispersing") 
may result upon the addition of a surfactant to an aqueous system 
containing the dispersant of this invention, when the dispersant is 
solubilized. 
In general, solvents and non-solvents (or mixtures of solvents, 
non-solvents other organics and volatiles) may be used to manipulate the 
viscosity or dispersibility of polymer containing systems. The 
co-thickening or co-dispersing with mineral spirits has utility in textile 
printing pastes, and in waterborne automotive basecoats. These systems 
usually contain mineral spirits (because of the pigments used therein), so 
that the mineral spirits provide an economical way of increasing viscosity 
or dispersibility and improving the efficiency of the thickener or 
dispersant. 
The dispersants and thickeners described herein are useful in a variety of 
aqueous systems, such as textile coatings (woven and nonwoven), latex 
paint formulations, cosmetic formulations, pigment dispersions and 
slurries, dentifrices, hand lotions, liquid detergents, quenchants, 
agricultural chemicals, concrete additives, transmission fluids, waste 
water treatment (flocculants), turbulent drag reduction, aircraft 
anti-icing, automation coatings (OEM and refinish), architectural 
coatings, industrial coatings, caulks, adhesives and the like. Other 
applications include, for example, paper coating, paper making, mineral 
processing, brine viscosification, superabsorbency, enhanced oil recovery, 
personal care products, biomedical, pharmaceutical and the like. 
Preferably, the polymeric dispersant is used to disperse and the polymeric 
thickener is used to thicken aqueous coating compositions, and more 
preferably latex paint compositions. Examples of suitable latex paint 
compositions include those based on resins or binders of acrylonitrile, 
copolymers of acrylonitrile wherein the comonomer is a diene like 
isoprene, butadiene or chloroprene, homopolymers and copolymers of 
styrene, homopolymers and copolymers of vinyl halide resins such as vinyl 
chloride, vinylidene chloride or vinyl esters such as vinyl acetate, vinyl 
acetate homopolymers and copolymers, copolymers of styrene and unsaturated 
acid anhydrides like maleic anhydrides, homopolymers and copolymers of 
acrylic and methacrylic acid and their esters and derivatives, 
polybutadiene, polyisoprene, butyl rubber, natural rubber, 
ethylene-propylene copolymers, olefins resins like polyethylene and 
polypropylene, polyvinyl alcohol, carboxylated natural and synthetic 
latices, epoxies, epoxy esters and similar polymeric latex materials. 
Latex paint compositions are well known in the art and typically comprise 
an emulsion, dispersion or suspension of discrete particles of resin 
binder and pigment in water. Optional ingredients typically include 
thickeners, antifoam agents, plasticizers, surfactants, coalescing agents, 
and the like. Associative dispersants may be used to advantage with 
associative thickeners in coating formulations as described below. 
The coating compositions can comprise cross-linking materials, pigments not 
capable of being associatively dispersed, dyes, optical brighteners and 
other dispersants. The coating compositions of this invention can also 
comprise biocides, bacteriocides, and defoamers, all conventionally 
employed in coating compositions. The usual additives are added in 
conventional amounts to obtain desired formulation properties. 
Mixtures of dispersants and/or thickeners may also be useful in this 
invention. For example, a polymeric dispersant of this invention may 
advantageously be used in combination with one or more other polymeric 
dispersants of this invention or one or more other polymeric dispersants, 
e.g., a polymeric dispersant containing only a macromonomer as described 
in U.S. Pat. Nos. 5,292,843, 5,292,828 or Reissue Pat No.33,156. Likewise, 
a polymeric thickener of this invention may advantageously be used in 
combination with one or more other polymeric thickeners of this invention 
or one or more other polymeric thickeners, e.g., a polymeric thickener 
containing only a macromonomer as described in U.S. Pat. Nos. 5,292,843, 
5,292,828 or Reissue Pat. No. 33,156. By using such mixtures, paint 
properties may be optimized and improvements in the manufacturing process 
may be realized. This invention is not intended to be limited in any 
manner by the permissible mixtures of dispersants, thickeners or 
dispersants and thickeners. 
The use of associative dispersants that contain complex hydrophobic groups 
that are similar to those used by associative thickeners allows the 
development of a "systems approach", wherein paint properties (hiding, 
color development, colorant compatibility, higher gloss, improved 
rheology, improved synerisis, improved viscosity stability) are optimized 
and improvements in the manufacturing process realized by using compatible 
associative hydrophobe technology in colorants, dispersants, pigment 
slurries, latexes, and thickeners in conventional, low, and zero VOC tint 
base and paint systems. Especially important to zero and low VOC colorants 
is the ability of the associative dispersant to provide improved pigment 
wetting, resistance to pigment settling, high solids pigment dispersion 
capability, and machine colorant dispersing (i.e., rheological 
properties). Mixtures of associative dispersants and associative 
thickeners are preferred mixtures of this invention. 
As used herein, the term "complex hydrophobe" is contemplated to include 
all permissible hydrocarbon compounds having 2 or more hydrophobe groups, 
e.g., bis-dodecylphenyl, bis-nonylphenyl, bis-octylphenyl and the like. 
For purposes of this invention, the term "hydrocarbon" is contemplated to 
include all permissible compounds having at least one hydrogen and one 
carbon atom. In a broad aspect, the permissible hydrocarbons include 
acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, 
aromatic and nonaromatic organic compounds which can be substituted or 
unsubstituted. 
As used herein, the term "substituted" is contemplated to include all 
permissible substituents of organic compounds unless otherwise indicated. 
In a broad aspect, the permissible substituents include acyclic and 
cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic 
and nonaromatic substituents of organic compounds. Illustrative 
substituents include, for example, alkyl, alkyloxy, aryl, aryloxy, 
hydroxy, hydroxyalkyl, amino, aminoalkyl, halogen and the like in which 
the number of carbons can range from 1 to about 20 or more, preferably 
from 1 to about 12. The permissible substituents can be one or more and 
the same or different for appropriate organic compounds. This invention is 
not intended to be limited in any manner by the permissible substituents 
of organic compounds.

The invention is illustrated by certain of the following examples. 
EXAMPLE 1 
Preparation of 1,3-Bis(nonylphenoxy)-2-propanol 
To a five neck, two liter round bottom flask equipped with an addition 
funnel, thermometer, nitrogen dispersant tube, mechanical stirrer, and a 
decanting head with a water-cooled condenser were added 220 grams (1.00 
mole) of nonylphenol and 250 milliliters of cyclohexane. The solution was 
then heated to reflux and 2.8 grams (1.3 wt. % based on nonylphenol) of 
potassium hydroxide in 10 milliliters of water was slowly added to the 
flask. After essentially all the water was recovered in the decanting head 
(10 milliliters + 1 milliliter formed), 250.7 grams (0.91 mole) of 
nonylphenyl glycidyl ether as added dropwise. During the addition of the 
glycidyl ether, the reaction temperature was maintained between 60.degree. 
and 80.degree. C. After the addition was complete, the solution was 
refluxed for four hours. The contents of the flask were then washed with a 
five percent aqueous solution of phosphoric acid, and the organic layer 
was separated from the water layer and washed twice with deionized water. 
The reaction mixture was then placed in a one liter round bottom flask, 
and the remaining cyclohexane and unreacted nonylphenol were recovered by 
distillation, first at atmospheric pressure, then under vacuum at 0.2 mm 
Hg. The kettle temperature was not allowed to exceed 180.degree. C. during 
the distillation to prevent discoloration of the product. The concentrated 
solution was then refiltered to give 425 grams of a pale-yellow liquid. 
End-group MW analysis gave a molecular weight of 506.8 (theoretical 
MW=496.8). Ir and nmr spectra were identical to previously recorded 
spectra for the compound. 
EXAMPLE 2 
Preparation of 5 Mole Ethoxylate of 1,3-Bis(nonylphenoxy)-2-propanol 
To a 500 milliliter, stainless steel, high pressure autoclave was charged 
200 grams (0.40 mole) of 1,3-bis(nonylphenoxy)-2-propanol, which contained 
a catalytic amount of the potassium salt of the alcohol as described in 
Example 1. After purging the reactor with nitrogen, the alcohol was heated 
to 130.degree. C. with stirring, and 86.9 grams (2.0 mole) of ethylene 
oxide was added over a two hour period. The reaction temperature and 
pressure were maintained from 130.degree. C. to 140.degree. C. and 60 psig 
during the course of the reaction. After the addition of ethylene oxide 
was complete, the reaction mixture was held at 140.degree. C. for an 
additional hour to allow all the ethylene oxide to cook out. The reaction 
mixture was dumped while hot, under nitrogen, and neutralized with acetic 
acid to yield 285 grams of a pale-yellow liquid. 
In a manner similar to that described in Example 2 and also in U.S. Pat. 
Nos. 5,292,843 and 5,292,828, other surfactants were prepared and are 
identified in Table A below. 
TABLE A 
______________________________________ 
##STR6## 
Surfactant Moles of 
Designation 
R.sub.1 R.sub.2 /R.sub.3 
Ethoxylation 
______________________________________ 
S-1 Nonylphenyl Hydrogen (R.sub.2) 
40 
S-2 Nonylphenyl Nonylphenyl (R.sub.3) 
40 
S-3 Nonylphenyl Nonylphenyl (R.sub.3) 
20 
S-4 Nonylphenyl Octylphenyl (R.sub.3) 
20 
S-5 Nonylphenyl Octylphenyl (R.sub.3) 
40 
S-6 Nonylphenyl Nonylphenyl (R.sub.3) 
80 
S-7 Nonylphenyl Nonylphenyl (R.sub.3) 
120 
S-8 Nonylphenyl Nonylphenyl (R.sub.3) 
6 
S-9 Nonylphenyl Nonylphenyl (R.sub.3) 
12 
S-10 n-Decyl Hydrogen (R.sub.2) 
40 
S-11 n-Dodecyl Hydrogen (R.sub.2) 
40 
S-12 n-Hexadecyl Hydrogen (R.sub.2) 
40 
S-13 n-Octadecyl Hydrogen (R.sub.2) 
40 
S-14 1-Eicosanyl Hydrogen (R.sub.2) 
40 
S-15 Methyl Hydrogen (R.sub.2) 
44 
S-16 Methyl Hydrogen (R.sub.2) 
113 
S-17 Octylphenyl Hydrogen (R.sub.2) 
40 
S-18 Dodecylphenyl 
Hydrogen (R.sub.2) 
40 
S-19 Dinonylphenyl 
Hydrogen (R.sub.2) 
40 
S-20 Nonylphenyl Hydrogen (R.sub.2) 
70 
S-21 Nonylphenyl Hydrogen (R.sub.2) 
50 
______________________________________ 
R.sub.2 = hydrogen or a R.sub.3 OCH.sub.2 residue. 
EXAMPLE 3 
Macromonomer Preparation 
To a 3 liter round bottom flask equipped with an overhead stirrer, nitrogen 
inlet and sparging tube, water cooled reflux condenser, monomer addition 
tube, FMI pump and feed tank, and heating mantel and temperature 
controller, 2000 grams of previously melted surfactant S-2 were charged. 
The materials were heated to 85.degree. C. under nitrogen sparge and 
mixing, and held at temperature for 1 hour to drive off residual water. 
Then 0.05 grams of 4-methoxyphenol were added, and the mixture was sparged 
with air for 15 minutes to activate the inhibitor. 2.4 grams of dibutyl 
fin dilaurate were added, and after 15 minutes of mixing, 201.25 grams of 
alpha, alpha-dimethyl-m-isopropenyl benzyl isocyanate (m-TMI) were fed 
over 45 minutes. The mixture was held at 85.degree. C. for another 4 
hours. Then 243 grams of water was pumped into the reaction mixture over a 
25 minute period to wash the feed lines of isocyanate, and to dilute the 
product macromonomer to 90% solids. The product macromonomer was cooled 
and collected in a 1 gallon jug. 
In a manner similar to that described in Example 3 and also in U.S. Pat. 
Nos. 5,292,843 and 5,292,828, other macromonomers were prepared using 
stoichiometric amounts of the surfactants and unsaturated compounds 
identified in Table B below. 
TABLE B 
______________________________________ 
Surfactant Macromonomer 
Designation 
Unsaturated Compound 
Designation 
______________________________________ 
S-1 m-TMI M-1 
S-2 m-TMI M-2 
S-3 m-TMI M-3 
S-4 m-TMI M-4 
S-5 m-TMI M-5 
S-6 m-TMI M-6 
S-7 m-TMI M-7 
S-2 Isocyanato Ethyl Methacrylate 
M-8 
S-5 Isocyanato Ethyl Methacrylate 
M-9 
S-1 Methacrylic Anhydride 
M-10 
S-2 Methacrylic Anhydride 
M-11 
S-5 Methacrylic Anhydride 
M-12 
S-6 Methacrylic Anhydride 
M-13 
S-2 Acrylic Anhydride M-14 
S-5 Acrylic Anhydride M-15 
S-6 Acrylic Anhydride M-16 
S-2 Crotonic Anhydride M-17 
S-5 Maleic Anhydride M-18 
S-2 Methacryloyl Isocyanate 
M-19 
S-6 Methacryloyl Isocyanate 
M-20 
S-8 m-TMI M-21 
S-9 m-TMI M-22 
S-10 m-TMI M-23 
S-11 m-TMI M-24 
S-12 m-TMI M-25 
S-13 m-TMI M-26 
S-14 m-TMI M-27 
S-15 m-TMI M-28 
S-16 m-TMI M-29 
S-17 m-TMI M-30 
S-18 m-TMI M-31 
S-19 m-TMI M-32 
S-20 m-TMI M-33 
S-21 m-TMI M-34 
Silwet m-TMI M-35 
L-7614* 
______________________________________ 
*Silwet L7614 is an ethoxylated silicone surfactant available from OSi 
Specialties, Inc. 
EXAMPLE 4 
Preparation Of An Alkali-Soluble Thickener 
A monomer mixture was prepared by charging 120 grams of ethyl acrylate 
(Aldrich), 120 grams of methacrylic acid (Aldrich), 13 grams of a 75% 
solution of Aerosol.RTM. OT surfactant (American Cyanamid), 45 grams of 
macromonomer M-6, 15 grams of macromonomer M-1, and 30 grams of distilled 
deionized water to a bottle, and mixing the contents with vigorous 
shaking. To a two liter jacketed resin flask equipped with a four-bladed 
stainless steel mechanical stirrer, Claisen connecting tube, Friedrichs 
water condenser, nitrogen sparge and bubble trap, thermometer, and monomer 
addition inlets 846 grams of water and 2.7 grams of a 75% solution of 
Aerosol.RTM. OT surfactant were added. Under nitrogen purge, the reaction 
was heated to 80.degree. C. by circulating temperature controlled water 
through the reactor jacket. 0.26 grams of sodium persulfate initiator 
(Aldrich) previously dissolved in 2.3 grams of water, and 35 grams of the 
monomer mixture were added to the reactor. The remainder of the monomer 
mixture was charged to a one-liter graduated monomer feed cylinder. In a 
separate vessel, 0.51 grams of sodium persulfate was dissolved in 50 grams 
of water. After allowing the initial monomer charge to react for 35 
minutes to form a seed latex, the remaining monomer feed mixture and the 
sodium persulfate solution were conveyed to the reaction vessel by FMI 
pumps via 1/8" Teflon tubing over a two and one-half hour period while the 
reaction mixture was continuously stirred at a reaction temperature held 
between 76.degree.-82.degree. C. The reaction was allowed to proceed for 
another quarter hour, after which 0.1 gram of tert-butyl hydroperoxide 
(Aldrich) previously dissolved in 1.4 grams of water and 0.1 grams of 
sodium formaldehyde sulfoxylate (Royce) previously dissolved in 4.6 grams 
of water were added to the latex to reduce residual monomer. The reaction 
was allowed to proceed for an additional 70 minutes. The thickening 
ability of the resulting product was monitored by Brookfield viscosity at 
6 rpm by diluting the 25% solids latex to 0.25%, 0.50% and 0.75% solids, 
and subsequently neutralizing the product to pH=9.0 with a 95% solution of 
2-amino-2-methyl-1-propanol (AMP-95, Angus Chemical Company). The results 
are given in Table C below. This thickener is designated as P-1 in Table 
C. 
EXAMPLES 5-53 
Preparation of Thickeners 
In a manner similar to that described in Example 4, other polymers were 
prepared using the monomers identified in Table C in the amounts 
identified in Table C. Examples 4 through 6 illustrate the use of a 
mixture of hydrophobes in a thickener that imparts a rheology similar to 
that obtained with conventional cellulosic thickeners. Examples 7, 9 and 
33 are illustrative of prior art thickeners that employ solely 
conventional hydrophobes. Example 8 is illustrative of thickeners 
employing complex hydrophobes. Examples 10 and 11 illustrate the use of a 
mixture of hydrophobes in a thickener that imparts a comparatively more 
Newtonian rheology to paints. Examples 12 through 15 illustrate the use of 
adducts of methacryloyl isocyanate. Examples 9 through 11 and 16 and 17 
illustrate the use M-6 and M-2, respectively, and that a surprising small 
amount of complex hydrophobe in the hydrophobe mixture can dramatically 
influence rheology. Examples 18 through 20 illustrate the use of 
comohomers besides ethyl acrylate. The following examples illustrate the 
use of the following hydrophobes in macromonomer mixtures: examples 21 and 
22--silicone hydrophobe in conjunction with a complex hydrophobe; examples 
23 through 29--methyl hydrophobes in conjunction with a complex 
hydrophobe; examples 30 through 33--conventional dinonylphenyl hydrophobes 
in conjunction with nonylphenyl hydrophobes; examples 34 through 
53--nonylphenyl hydrophobe in conjunction with complex hydrophobe and in 
combination with SEM and a chain transfer agent other than tDDM. As used 
in Table C, the following abbreviations have the indicated meanings: 
MM=Macromonomer; EA=Ethyl Acrylate; MAA=Methacrylic Acid; 
2-EHMP=2-Ethylhexyl Mercapto Propionate; 2-SEM=2-sulfoethyl methacrylate; 
CTA=chain transfer agent; tDDM=tertiary dodecanethiol; BA=Butyl Acrylate. 
TABLE C 
__________________________________________________________________________ 
Thickener Composition by 
Weight Brookfield Viscosity 
Macromonomers % MM CTA* (CPS) @ pH = 9.0 
Thickener 
Example 
#1 #2 #1 #2 % EA 
% MAA 
% Other 
p.h.r. 0.25% 
0.50% 
0.75% 
Designation 
__________________________________________________________________________ 
4 M-1 M-6 5 15 40 40 0 0 122 35,700 
132,400 
P-1 
5 M-1 M-6 10 10 40 40 0 0 107 19,100 
70,300 
P-2 
6 M-1 M-6 15 5 40 40 0 0 90 8,860 
32,900 
P-3 
7 M-1 M-6 20 0 40 40 0 0 65 355 1,275 
P-4 
8 M-1 M-6 0 20 40 40 0 0 120 43,000 
150,000 
P-5 
9 M-34 M-6 15 0 50 35 0 0.2 (tDDM) 
-- 12 46 P-6 
10 M-34 M-6 13 2 50 35 0 0.2 (tDDM) 
-- 161 450 P-7 
11 M-34 M-6 10 5 50 35 0 0.2 (tDDM) 
-- 1,760 
10,260 
P-8 
12 M-1 M-20 
5 15 40 40 0 0 850 44,200 
120,000 
P-9 
13 M-1 M-20 
10 10 40 40 0 0 455 25,700 
59,000 
P-10 
14 M-1 M-20 
15 5 40 40 0 0 175 9,160 
22,800 
P-11 
15 M-1 M-20 
10 10 40 40 0 0.1 (2EHMP) 
440 14,700 
36,700 
P-12 
16 M-34 M-2 13 2 50 35 0 0.2 (tDDM) 
-- 151 800 P-13 
17 M-34 M-2 10 5 50 35 0 0.2 (tDDM) 
-- 655 10,600 
P-14 
18 M-34 M-2 13 2 40 35 10 (BA) 
0.2 (tDDM) 
-- 33 247 P-15 
19 M-34 M-2 13 2 30 35 20 (BA) 
0.2 (tDDM) 
-- 15 115 P-16 
20 M-34 M-2 13 2 20 35 30 (BA) 
0.2 (tDDM) 
-- -- 34 P-17 
21 M-35 M-6 20 0 40 40 0 0 166 2,010 
6,340 
P-18 
22 M-35 M-6 18 2 40 40 0 0 250 6,860 
19,000 
P-19 
23 M-29 M-2 20 0 40 40 0 0 31 250 710 P-20 
24 M-29 M-2 19 1 40 40 0 0 28 313 7,100 
P-21 
25 M-29 M-2 18 2 40 40 0 0 27 500 15,140 
P-22 
26 M-29 M-2 15 5 40 40 0 0 17 620 17,500 
P-23 
27 M-29 M-2 10 10 40 40 0 0 38 5,140 
67,000 
P-24 
28 M-29 M-2 5 10 45 40 0 0 64 6,440 
68,000 
P-25 
29 M-29 M-2 20 10 30 40 0 0 20 2,575 
50,000 
P-26 
30 M-32 M-34 
30 0 30 40 1 (SEM) 
0.3 (tDDM) 
25 50 125 P-27 
31 M-32 M-34 
30 2 30 40 0.5 (SEM) 
0.3 (tDDM) 
10 30 90 P-28 
32 M-32 M-34 
30 5 30 40 0.5 (SEM) 
0.3 (tDDM) 
4 7 37 P-29 
33 M-32 M-34 
30 0 30 40 0 0 -- -- -- P-30 
34 M-34 M-6 0 10 50 40 1 (SEM) 
0.3 (2EHMP) 
10 10 15 P-31 
35 M-34 M-6 0 10 50 40 1 (SEM) 
0 1,000 
12,500 
14,500 
P-32 
36 M-34 M-6 0 20 50 40 1 (SEM) 
0 20 9,000 
28,500 
P-33 
37 M-34 M-6 0 15 45 40 1 (SEM) 
0.15 25 4,000 
23,500 
P-34 
(2EHMP) 
38 M-34 M-6 0 20 40 40 1 (SEM) 
0.3 (3EHMP) 
50 2,000 
7,000 
P-35 
39 M-34 M-6 15 0 45 40 1 (SEM) 
0.15 25 100 200 P-36 
(2EHMP) 
40 M-34 M-6 20 0 40 40 1 (SEM) 
0 50 1,000 
2,500 
P-37 
41 M-34 M-6 10 0 50 40 1 (SEM) 
0 50 325 1,275 
P-38 
42 M-34 M-6 20 0 40 40 1 (SEM) 
0.3 (2EHMP) 
-- -- 5 P-39 
43 M-34 M-6 10 0 50 40 1 (SEM) 
0.3 (2EHMP) 
-- -- 10 P-40 
44 M-34 M-6 10 10 40 40 1 (SEM) 
0.15 175 11,000 
21,000 
P-41 
(2EHMP) 
45 M-34 M-6 5 5 50 40 1 (SEM) 
0.15 -- 20 50 P-42 
(2EHMP) 
46 M-34 M-6 7.5 
7.5 
45 40 1 (SEM) 
0.15 10 175 625 P-43 
(2EHMP) 
47 M-34 M-6 7.5 
7.5 
45 40 1 (SEM) 
0 1275 
10,000 
40,500 
P-44 
48 M-34 M-6 9.4 
3.1 
47.5 
40 1 (SEM) 
0.1 (2EHMP) 
50 425 1175 P-45 
49 M-34 M-6 13.1 
4.4 
42.5 
40 1 (SEM) 
0.1 (2EHMP) 
450 2,725 
8,500 
P-46 
50 M-34 M-6 7.5 
7.5 
45 40 1 (SEM) 
0.3 (2EHMP) 
30 1,200 
11,500 
P-47 
51 M-34 M-6 4.4 
13.1 
42.5 
40 1 (SEM) 
0.2 (2EHMP) 
10 50 150 P-48 
52 M-34 M-6 0 12.5 
47.5 
40 1 (SEM) 
0.1 (2EHMP) 
400 13,500 
44,500 
P-49 
53 M-34 M-6 7.7 
7.5 
45 40 1 (SEM) 
0.05 300 12,700 
32,500 
P-50 
(2EHMP) 
__________________________________________________________________________ 
*CTA = Chain Transfer Agent used, part per hundred parts of resin. 
EXAMPLES 54 THROUGH 71 
Colorant Compatibility and Stability of Vinyl Acrylic Paints 
A vinyl acrylic semi-gloss paint (Example 54 in Table D below) was prepared 
by mixing the following ingredients in sequence: 91 grams of water, 2 
grams of Tamol.RTM. 1124 (Rohm and Haas), 2 grams of Triton.RTM. N-101 
(Union Carbide Corp.), 20 grams of Omyacarb.RTM. UF (Omya Inc.), 275 grams 
of TiPure.RTM. R-942 (DuPont), 2 grams (a first portion) of Drewplus.RTM. 
L-475 (Ashland), 441 grams of UCAR.RTM. Latex 367 (Union Carbide Corp.), 
17 grams of UCAR.RTM. Filmer IBT (Union Carbide Corp.), 4 grams of 
AMP-95.RTM. (Angus), 2 grams of Nuosept.RTM. 95 (Huls), 1 gram of 
Triton.RTM. GR-5M (Union Carbide Corp.), 4 grams (a second portion) of 
Drewplus.RTM. L-475, and 11.91 grams of thickener P-6. Other paints 
identified in Table D were prepared in a similar manner. In particular, 
one thickener selected from the group of thickeners that imparted a 
rheology similar to a conventional cellulosic thickener (i.e., P-1, P-2, 
P-3, P-4, P-5, P-30) and one thickener selected from the group of 
thickeners that imparted a more Newtonian rheology (i.e., P-6, P-7, P-8) 
were used in combination in the paint to provide the appropriate balance 
of low, middle, and high shear rate viscosities. The amount and type of 
thickener solids in the solution, identified in Table D, were selected to 
produce a paint with a Stormer viscosity of 91 KU after an equilibration 
time of one day. After equilibration, the rheological properties recorded 
in Table D (0.3 RPM Brookfield Viscosity, Stormer Viscosity, ICI 
Viscosity) were measured. 
To determine colorant float (i.e., in-can separation) and flocculation, 
12.5 grams of black colorant (Huls) were added under agitation to 256 
grams of equilibrated paint, and the paints were aged 1 week. Colorant 
float was determined by visually inspecting the degree of separation as 
manifested by an oily layer containing a high concentration of colorant, 
appearing richer in color than the rest of the paint. The subjective 
rating ranges from no separation (None) though very slight (VSL), slight 
(SL), moderate (MOD), poor (POOR), and severe (SEV). Colorant flocculation 
was determined by drawing down a 3 mil paint film on a Leneta 3B chart. 
After allowing the film to dry overnight, a small amount of paint was 
applied with the tip of a finger on the dry film and rubbed in a circular 
motion until dry. Rubbing the paint in this way applies shear to the paint 
as it dried to prevents the pigment from flocculating, and indicates the 
true color of the paint with well dispersed pigment. Comparing the color 
of the rubbed-up spot to the rest of the film reveals colorant 
flocculation. If the colorant has fiocculated, the paint film has less 
color than the rubbed-up spot. If the titanium dioxide has fiocculated, 
the paint film has more color than the rubbed-up spot. The degree of 
flocculation was rated subjectively from none (None) though very slight 
(VSL), slight (SL), moderate (MOD), poor (POOR), and severe (SEV). 
Paint examples 54, 55 and 56 were thickened with polymers representing the 
prior art. Although it is possible to achieve either color acceptance or 
stability against in-can float individually, the prior art thickeners 
employing conventional hydrophobes do not impart stability against pigment 
flocculation or against in-can colorant float simultaneously. Use of the 
prior art thickeners in combination to achieve the desired rheological 
properties exasperates the color flocculation and color float problems 
(see example 56). But a thickener employing a complex hydrophobe (but not 
a mixture of hydrophobes) produces better color acceptance and in-can 
float when used in combination with a thickener employing conventional 
hydrophobes (but not a mixture of hydrophobes) (see example 57). 
However, even better color acceptance and stability against in-can colorant 
float can be achieved when each thickener employs a mixture of 
hydrophobes, especially when the hydrophobe mixture contain a complex 
hydrophobe (see examples 62 and 64). 
The amount of thickener blend and the ratio of thickeners used in the blend 
is approximately constant for the examples 57 through 71. Even though all 
of the paints required about the same amount of thickener blend to achieve 
the required Stormer viscosity, the low shear and high shear viscosities 
varied from 400 to 2000 Poise, and 0.9 to 1.7 Poise, respectively, for a 
2.times.change in ICI viscosity, and a 5.times.change in low shear 
viscosity. Thus, the use of a mixture of hydrophobes in a given thickener 
permits manipulation of low and high shear viscosities independent of the 
molecular weight of the polymer, and therefore allows manipulation of 
rheology without harming color acceptance, as desired. 
The examples in Table D show that the selection of composition of the 
hydrophobes in the hydrophobe mixture employed by the thickener, as well 
as the selection of the thickeners to be used in combination to thicken 
the latex paint are important, and that the improved stability against 
in-can float and colorant and pigment flocculation are fundamentally 
related to the physical chemistry of hydrophobic interactions. 
TABLE D 
__________________________________________________________________________ 
Example # 54 55 56 57 58 59 60 61 62 
__________________________________________________________________________ 
Thickener P-6 P-6 P-6 P-7 P-8 P-6 P-7 P-8 
Amount (grams) 
11.91 5.62 2.91 2.82 2.62 2.98 2.84 2.75 
Thickener P-30 P-30 P-5 P-5 P-5 P-1 P-1 P-1 
Amount (Grams) 4.59 2.65 2.87 2.78 2.57 3.04 2.81 2.75 
Viscosity 0.3 RPM 
396 1236 784 2128 2092 1940 1776 1736 1776 
(Poise) 
Viscosity 60 RPM 
21 38 31 34 38 38 34 34 42 
(Poise) 
ICI Viscosity (Poise) 
3.05 1.10 2.10 1.10 1.00 0.90 1.20 1.20 0.95 
Stormer Viscosity 
90 91 97 91 91 90 91 89 91 
(KU) 
Color Flocculation: 
1 Day VSL MOD MOD SL-MOD 
VSL-SL 
VSL MOD SL SL 
1 Week VSL MOD MOD SL-MOD 
SL VSL-SL 
SL-MOD 
MOD SL 
2 Weeks SL MOD MOD- MOD SL-MOD 
SL MOD MOD SL 
POOR 
4 Weeks VSL MOD POOR MOD SL-MOD 
VSL-SL 
MOD MOD SL 
In-Can Float: 
1 Day POOR SL MOD VSL SL SL SL SL SL 
1 Week POOR SL MOD SL VSL SL SL SL SL 
2 Weeks MOD SL SL SL SL SL SL SL SL 
4 Weeks POOR SL-MOD 
POOR SL MOD MOD SL SL SL 
__________________________________________________________________________ 
Example # 63 64 65 66 67 68 69 70 71 
__________________________________________________________________________ 
Thickener P-6 P-7 P-8 P-6 P-7 P-8 P-6 P-7 P-8 
Amount (grams) 
3.18 3.18 2.81 3.21 3.12 2.86 3.26 3.28 2.94 
Thickener P-2 P-2 P-2 P-3 P-3 P-3 P-4 P-4 P-4 
Amount (Grams) 
3.32 3.18 2.99 3.23 3.09 2.83 3.34 3.40 2.85 
Viscosity 0.3 RPM 
1352 1368 1416 856 896 936 140 484 740 
(Poise) 
Viscosity 60 RPM 
35 39 41 32 35 33 26 28 35 
(Poise) 
ICI Viscosity (Poise) 
1.40 1.30 1.05 1.70 1.30 1.15 1.70 1.45 1.15 
Stormer Viscosity 
91 91 91 91 91 90 90 90 90 
(KU) 
Color Flocculation: 
1 Day SL SL SL SL SL-MOD 
SL SL SL MOD 
1 Week SL-MOD 
SL SL-MOD 
SL-MOD 
MOD SL-MOD 
SL MOD MOD 
2 Weeks MOD SL MOD MOD MOD MOD SL-MOD 
MOD MOD 
4 Weeks SL-MOD 
SL SL-MOD 
SL-MOD 
MOD SL-MOD 
SL-MOD 
SL MOD 
In-Can Float: 
1 Day SL SL SL SL SL SL SL SL SL 
1 Week SL SL SL SL SL SL SL SL SL 
2 Weeks SL SL SL SL SL SL SL SL SL 
4 Weeks MOD SL MOD MOD MOD MOD MOD MOD MOD 
__________________________________________________________________________ 
EXAMPLE 72 
Preparation of Dispersant 
In a manner similar to that described in Example 4, a polymeric dispersant 
was prepared using the monomers identified in Table E below in the amounts 
identified in Table E. The %AM, %MAA and %EA columns of Table E refer to % 
by weight of AM, MAA and EA in the dispersant composition. The polymer 
product had a weight average molecular weight of 9050 and a number average 
molecular weight of 4730 as measured by gel permeation chromatography in 
tetrahydrofuran solvent. 
TABLE E 
______________________________________ 
% % % phr phr 
Designation 
AM** AM MAA EA 2-EHMP SEM 
______________________________________ 
P-51 M-1/M11 10/10 30 50 4 0 
______________________________________ 
phr = parts per hundred parts resin. 
**See Table B. 
EXAMPLE 73 
Preparation Of High Solids Titanium Dioxide Slurry 
To 2796 grams of solid R-902 titanium dioxide pigment powder (DuPont) was 
added 774 grams of water, 34 grams of sodium hydroxide (35% solids 
solution), 379 grams of 24.08% solids of dispersant P-51 in the latex 
form, and 10 grams of Drewplus.RTM. L-475 defoamer (Drew Industrial 
Division Of Ashland Chemical). This mixture was ground on a high speed 
disperser for 15 minutes, which was sufficient to provide an excellent 
degree of dispersion as verified by the grind check paste method. Table F 
reports the total solids of the slurry. 
The grind check method consists of mixing the pigment slurry at 1:5 ratio 
with a "grind check paste" consisting of the following: 445 grams of 3.5% 
by weight solution of Natrosol.RTM. 250HBR (Hercules), 350 grams of 
UCAR.RTM. latex 367 (Union Carbide Corp.), 3 grams of Drewplus.RTM. L-475, 
1.5 grams of Nuosept.RTM. 95 preservative (Huls), and 17 grams of pathalo 
blue paste. The grind check paste was added to the pigment slurry under 
agitation until well mixed, after which a 3 mil film was drawn-down on a 
plain white chart and allowed to dry in an oven for 10-15 minutes. 
Scratching the dry film with a razor blade revealed any undispersed 
pigment aggregates as a white streak: the larger the streak, the larger 
the pigment agglomerate. A film having an excellent degree of dispersion 
has no white streaks. 
TABLE F 
______________________________________ 
Titanium Dioxide Slurry 
______________________________________ 
% Titanium Dioxide Solids 
68.38 
% Dispersant Solids 2.23 
% Defoamer 0.3 
% Sodium Hydroxide 0.3 
Theo. Slurry Solids % 70.22 
Actual Slurry Solids % 
70.22 
Dispersant Solids on Pigment % 
3.25 
______________________________________ 
EXAMPLE 74 
Colorant Compatibility And Stability Of Vinyl Acrylic Paint 
A vinyl acrylic semi-gloss paint was prepared by mixing the following 
ingredients in sequence: 75.22 grams of water, 2 grams of Triton.RTM. 
N-101 (Union Carbide Corp.), 20 grams of Omyacarb.RTM. UF, 306.12 grams of 
the slurry prepared in Example 73, 2 grams (a first portion) of L-475 
defoamer, 441 grams of UCAR.RTM. 367 Latex (Union Carbide Corp.), 17 grams 
of UCAR.RTM. IBT Filmer (Union Carbide Corp.), 4 grams of AMP-95.RTM. 
(Angus), 2 grams of Nuosept.RTM. 95, 1 gram of Triton.RTM. GR-5M (Union 
Carbide Corp.), 4 grams (a second portion) of L-475 defoamer, 16 grams 
(25% solids) of UCAR.RTM. Polyphobe 102 latex (Union Carbide Corp.), 16 
grams (25% solids) of UCAR.RTM. Polyphobe 104 latex (Union Carbide Corp.), 
147 grams of water, and 2 grams of 50% sodium hydroxide solution. 50 grams 
of a red-iron oxide (called ROX in Table G below), blue, or black colorant 
(Huls) were added under agitation for use in the colorant float and 
compatibility study. 
The paint was then characterized by rheological properties (0.3 RPM 
Brookfield Viscosity, Stormer Viscosity, ICI Viscosity), viscosity 
stability over time after storage at room temperature and at 140.degree. 
F. over a 4 week period, in-can separation (colorant float) over a 4 week 
period, and colorant flocculation over a 4 week period. Colorant float was 
determined by visually inspecting the degree of separation as manifested 
by an oily layer containing a high concentration of colorant, appearing 
richer in color than the rest of the paint. The subjective rating ranges 
from no separation (None) though very slight (VSL), slight (SL), moderate 
(MOD), poor (POOR), and severe (SEV). Colorant flocculation was determined 
by drawing down a 3 mil paint film on a Leneta 3B chart. After allowing 
the film to dry overnight, a small amount of paint was applied with the 
tip of a finger on the dry film and rubbed in a circular motion until dry. 
Rubbing the paint in this way applies shear to the paint as it dried to 
prevents the pigment from flocculating, and indicates the true color of 
the paint with well dispersed pigment. Comparing the color of the 
rubbed-up spot to the rest of the film reveals colorant flocculation. If 
the colorant has flocculated, the paint film has less color than the 
rubbed-up spot. If the titanium dioxide has fiocculated, the paint film 
has more color than the rubbed-up spot. The degree of flocculation was 
rated subjectively from none (None) though very slight (VSL), slight (SL), 
moderate (MOD), poor (POOR), and severe (SEV). The example in Table G 
shows that use of associative dispersant greatly improves the colorant 
float and flocculation, especially when used in combination with 
thickeners utilizing compatible or similar hydrophobes to those used by 
the associative dispersant. 
TABLE G 
______________________________________ 
Paint Properties 
______________________________________ 
Flocculation 1 Day 
ROX None 
Blue None 
Black None 
Flocculation 1 Wks. 
ROX None 
Blue N-VSL-TiO.sub.2 
Black None 
Flocculation 2 Wks. 
ROX VSL 
Blue VSL-TiO.sub.2 
Black N-VSL 
Flocculation 4 Wks. 
ROX VSL 
Blue VSL-TiO.sub.2 
Black N-VSL 
Brook/ICI 1 Day 
Brook/0.3/sp#=3 244 
Brook/60/sp#=4 28 
ICI 2.1 
Stormer (RT) 88 
In-Can Separation 24 HR 
ROX MOD 
Blue SL-MOD 
Black SL-MOD 
In-Can Separation 1 Wks 
ROX MOD 
Blue MOD 
Black MOD 
In-Can Separation 2 Wks 
ROX MOD 
Blue MOD 
Black MOD 
In-Can Separation 4 Wks 
ROX MOD 
Blue SL-MOD 
Black SL-MOD 
Paint Base Stormer 
Initial 88 
24 HR RT 88 
2 WK RT 94 
2 WK HS 90 
4 WK RT 95 
4 WK HS 92 
pH Stability 
Initial 9.1 
24 HR RT 8.85 
2 WK RT 8.15 
2 WK HS 7.7 
4 WK RT 9.5 
4 WK HS 7.54 
______________________________________ 
Although the invention has been illustrated by certain of the preceding 
examples, it is not to be construed as being limited thereby; but rather, 
the invention encompasses the generic area as hereinbefore disclosed. 
Various modifications and embodiments can be made without departing from 
the spirit and scope thereof.