Polymers are disclosed which comprise: PA1 (A) about 1-99.9 weight percent of one or more alpha, beta-monoethylenically unsaturated carboxylic acids, typically methacrylic acids; PA1 (B) about 0-98.9 weight percent of one or more monoethylenically unsaturated monomers, typically ethyl acrylate; PA1 (C) about 0.1-99 weight percent of one or more monoethylenically unsaturated macromonomers, and PA1 (D) about 0-20 weight percent or greater of one or more polyethylenically unsaturated monomers. These polymers can be solubilized in water with the aid of an alkali, like ammonium hydroxide. When the polymers are added to latex paints and neutralized, the viscosity of the paint is increased, brush drag is increased, and the paint rheology is otherwise improved.

BRIEF SUMMARY OF THE INVENTION 
1. Technical Field 
This invention relates to polymers which are soluble in, or swelled by, an 
aqueous alkaline medium to provide thickeners for use in aqueous coating 
compositions, especially latex paints. 
2. Background of the Invention 
Thickeners for aqueous systems are needed for various purposes, such as for 
architectual coatings, industrial coatings, automotive coatings and the 
like to improve rheology of the coatings. Hydroxyethyl cellulose is a well 
known thickener for aqueous systems, but it has various deficiencies in 
that excessive amounts must be used and the theology of the thickened 
system is inadequate. Various ethoxylated carboxyl-functional polymers 
which form alkali soluble thickeners are also known, but these have 
various deficiencies, including inadequate hydrolytic stability. 
It has long been desired to provide superior thickeners for aqueous systems 
which are highly efficient, which better resist hydrolysis, and which 
provide better rheology. This is achieved herein by providing new polymers 
which possess these desired characteristics. 
DISCLOSURE OF THE INVENTION 
This invention relates in part to polymers comprising: 
(A) about 1-99.9, preferably about 10-70, weight percent of one or more 
alpha, beta-monoethylenically unsaturated carboxylic acids, typically 
methacrylic acid; 
(B) about 0-98.9, preferably about 30-85, weight percent of one or more 
monoethylenically unsaturated monomers, typically ethyl acrylate; 
(C) about 0.1-99, preferably about 5-60, weight percent of one or more 
monoethylenically unsaturated macromonomers; and 
(D) about 0-20, preferably about 0-10, weight percent or greater of one or 
more polyethylenically unsaturated monomers, typically trimethylol propane 
triacrylate. 
This invention also relates in part to an emulsion of the above-identified 
polymer in water, which emulsion is useful as a thickening agent in 
aqueous compositions. In order to obtain the thickening effect, the 
polymer is dissolved in the aqueous composition to be thickened. 
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 polymer to an 
aqueous composition and dissolving the polymer in the aqueous composition. 
DETAILED DESCRIPTION 
A large proportion of one or more alpha, beta-monoethylenically 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. 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, 
.alpha.-chlorovinyl phenyl ether, vinyl .beta.-naphthyl ether, 
methacryonitrile, acrylamide, methacrylamide, N-alkyl acrylamides, N-aryl 
acrylamides, N-vinyl pyrrolidone, N-vinyl-3-morpholinones, 
N-vinyl-oxazolidone, N-vinyl-imidazole and the like including mixtures 
thereof. 
The macromonomers useful in this invention 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 macromonomer compounds useful in this invention can be prepared by a 
number of conventional processes, except for inclusion of the complex 
hydrophobe compounds described herein. Illustrative processes a re 
described, for example, in U.S. Pat. Nos. 4,514,552, 4,600,761, 4,569,965, 
4,384,096, 4,268,641, 4,138,381, 3,894,980, 3,896,161, 3,652,497, 
4,509,949, 4,226,754, 3,915,921, 3,940,351, 3,035,004, 4,429,097, 
4,421,902, 4,167,502, 4,764,554, 4,616,074, 4,464,524, 3,657,175, 
4,008,202, 3,190,925, 3,794,608, 4,338,239, 4,939,283 and 3,499,876. The 
macromonomers can also be prepared by methods disclosed in copending U.S. 
patent application Ser. No. (D-17010), which is incorporated herein by 
reference. 
Illustrative substituted and unsubstituted divalent hydrocarbon residues 
represented by R.sup.2 in formula I above include those described for the 
same type of substituents in formulae (i) and (ii) below. Illustrative 
substituted and unsubstituted monovalent hydrocarbon residues represented 
by R.sup.4, R.sup.5 and R.sup.6 in formula I above include those described 
for the same type of substituents in formula (i) and (ii) below. 
Illustrative R.sup.3 substituents include, for example, the organic residue 
of ethers, esters, urethanes, amides, ureas, urethanes, anhydrides and the 
like including mixtures thereof. The R.sup.3 substituent 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 (I) 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 a particular substituent for all positive values of z can be the same 
or different. 
The complex hydrophobe compounds having at least one active hydrogen useful 
in preparing the macromonomer compounds useful in this invention can be 
represented by the formula: 
##STR2## 
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. For purposes of the polymers and 
macromonomers of formula (I) above, when z is a value of 0 and R.sup.1 is 
the residue of a complex hydrophobe of formula (i) in which R.sub.1 is 
hexadecyl, a is a value of 1, R.sub.2 is tetradecyl, b is a value of 0, 
R.sub.3 is 
##STR3## 
R.sub.4 is --CH.sub.2 CH(tetradecyl)--, x is a value of 1, R.sub.5 is 
--CH.sub.2 CH.sub.2 --, y is a value of 34, R.sub.6 is hydrogen, and the 
--R.sup.3 --(R.sup.4)C.dbd.CR.sup.5 R.sup.6 portion of the macromonomer is 
the residue of maleic anhydride, then the polymers of this invention are 
other than a terpolymer of said macromonomer, styrene and maleic 
anhydride. Also for purposes of the polymers and macromonomers of formula 
(I) above, when R.sup.2 is --CH.sub.2 CH.sub.2 --, z is a value of 34 and 
R.sup.1 is the residue of a complex hydrophobe of formula (i) in which 
R.sub.1 is hexadecyl, a is a value of 1, R.sub.2 is tetradecyl, b is a 
value of 0, R.sub.3 is 
##STR4## 
R.sub.4 is --CH.sub.2 CH(tetradecyl)--, x is a value of 1, y is a value of 
0, R.sub.6 is hydrogen, and the --R.sup.3 --(R.sub.4)C.dbd.CR.sup.5 
R.sup.6 portion of the macromonomer is the residue of maleic anhydride, 
then the polymers of this invention are other than a terpolymer of said 
macromonomer, styrene and maleic anhydride. 
Other complex hydrophobe compounds having at least one active hydrogen 
useful in preparing the macromonomer compounds useful in this invention 
can be represented by the formula: 
##STR5## 
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. 
Illustrative substituted and unsubstituted monovalent hydrocarbon residues 
contain from 1 to about 50 carbon atoms or greater and are selected from 
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. The permissible hydrocarbon residues may contain fluorine, 
silicon, or other non-carbon atoms. 
Preferably, the substituted and unsubstituted hydrocarbon residues are 
selected from alkyl and aryl radicals which contain from about 1 to 30 
carbon atoms or greater. More preferably, the alkyl radicals contain from 
1 to 18 carbon atoms, while the aryl, arylalkyl, alkylaryl and cycloalkyl 
radicals preferably contain from 6 to 18 carbon atoms or greater. 
In a preferred embodiment of this invention, R.sub.1, R.sub.2, R.sub.7 and 
R.sub.8 can individually be a hydrocarbon radical represented by the 
formula: 
##STR6## 
wherein R.sub.16 and R.sub.17 are as defined for R.sub.1, R.sub.2, R.sub.7 
and R.sub.8 above, h and i are the same or different and are a value of 0 
or 1, and R.sub.18 is as defined for R.sub.3 above. For compounds 
represented by formulae (i) and (ii), it is understood that each formula 
(iii) radical in a given compound may be the same or different and the 
R.sub.16 and/or R.sub.17 groups may themselves be a formula (iii) radical 
to provide complex hydrophobes of a dendritic or of a cascading nature as 
described below. Further, R.sub.4, R.sub.5, R.sub.10 and R.sub.13 can 
individually be a hydrocarbon radical represented by the formula: 
EQU --CH[(OR.sub.19).sub.j OR.sub.20 ]-- (iv) 
wherein R.sub.19 is as defined for R.sub.4, R.sub.5, R.sub.10 and R.sub.13 
above, R.sub.20 is as defined for R.sub.6, R.sub.11 and R.sub.14 above, 
and j is a value of 0 or greater. 
Illustrative ionic substituents for R.sub.6, R.sub.11, R.sub.14 and 
R.sub.20 include cationic and anionic substituents such as sulfates, 
sulfonates, phosphates and the like. R.sub.6, R.sub.11, R.sub.14 and 
R.sub.20 may preferably be an organic residue containing 1 or more 
hydroxyls or nitrogen derivatives or epoxides or other reactive groups 
which may or may not contain unsaturation. 
Other illustrative terminal groups which are described by R.sub.6, 
R.sub.11, R.sub.14 and R.sub.20 include, for example, hydrocarbon residues 
which may contain allylic or vinylic unsaturation, acrylic or methacrylic 
functionality, styryl or alpha-methylstyryl functionality, and the like, 
such as the reaction product between the terminal alcohol (R.sub.6, 
R.sub.11, R.sub.14 and R.sub.20 =H) and glycidyl methacrylate, 
isocyanatoethyl methacrylate, alpha, alpha-dimethyl-m-isopropenyl benzyl 
isocyanate (m-TMI), and the like. Other examples of terminal groups may 
include hydrocarbon residues of alkyl, aryl, aralkyl, alkaryl, and 
cycloalkyl radicals which may or may not be substituted with one or more 
of the following: hydroxyl, carboxyl, isocyanato, amino, mono- or 
disubstituted amino, quaternary ammonium, sulfate, sulfonate, phosphate, 
epoxy, and the like and may or may not contain other non-carbon atoms 
including silicon or fluorine. Also included can be divalent siloxy 
radicals. Other nonhydrocarbon terminal groups may include sulfates, 
phosphates, and the like. 
Illustrative divalent hydrocarbon residues represented by R.sub.3, R.sub.4, 
R.sub.5, R.sub.9, R.sub.10, R.sub.12, R.sub.13, R.sub.15, R.sub.18 and 
R.sub.19 in the above formulae include substituted and unsubstituted 
radicals selected from alkylene, -alkylene-oxy-alkylene-, 
-arylene-oxy-arylene-, arylene, alicyclic radicals, phenylene, 
naphthylene, -phenylene-(CH.sub.2).sub.m (Q).sub.n (CH.sub.2).sub.m 
-phenylene- and -naphthylene-(CH.sub.2).sub.m (Q).sub.n (CH.sub.2).sub.m 
-naphthylene- radicals, wherein Q individually represents a substituted or 
unsubstituted divalent bridging group selected from --CR.sub.21 R.sub.22 
--, --O--, --S--, --NR.sub.23 --, --SiR.sub.24 R.sub.25 -- and --CO--, 
wherein R.sub.21 and R.sub.22 individually represent a radical selected 
from hydrogen, alkyl of 1 to 12 carbon atoms, phenyl, tolyl and anisyl; 
R.sub.23, R.sub.24 and R.sub.25 individually represent a radical selected 
from hydrogen and methyl, and each m and n individually have a value of 0 
or 1. More specific illustrative divalent radicals represented by R.sub.3, 
R.sub. 4, R.sub.5, R.sub.9, R.sub.10, R.sub.12, R.sub.13, R.sub.15, 
R.sub.18 and R.sub.19 include, e.g., 1,1-methylene, 1,2-ethylene, 
1,3-propylene, 1,6-hexylene, 1,8-octylene, 1,12-dodecylene, 1,4-phenylene, 
1,8-napthylene, 1,1'-biphenyl-2,2'-diyl, 1,1'-binaphthyl-2,2'-diyl, 
2,2'-binaphthyl-1,1'-diyl and the like. The alkylene radicals may contain 
from 2 to 12 carbon atoms or greater, while the arylene radicals may 
contain from 6 to 18 carbon atoms or greater. Preferably, R.sub.3, 
R.sub.4, R.sub.5, R.sub.9, R.sub.10, R.sub.12, R.sub.13, R.sub.15, 
R.sub.18 and R.sub.19 are an alkylene or arylene radical. The permissible 
divalent hydrocarbon residues may contain fluorine, silicon, or other 
non-carbon atoms. 
Illustrative trivalent hydrocarbon residues represented by R.sub.3, 
R.sub.9, R.sub.12 and R.sub.18 in the above formulae include substituted 
and unsubstituted radicals selected from 
##STR7## 
and the like, wherein R.sub.26 is a substituted or unsubstituted 
monovalent hydrocarbon residue as described herein and R.sub.27 is a 
substituted or unsubstituted divalent hydrocarbon residue as described 
herein. 
Of course, it is to be further understood that the hydrocarbon residues in 
the above formulae may also be substituted with any permissible 
substituent. Illustrative substituents include radicals containing from 1 
to 18 carbon atoms such as alkyl, aryl, aralkyl, alkaryl and cycloalkyl 
radicals; alkoxy radicals; silyl radicals such as --Si(R.sub.28).sub.3 and 
--Si(OR.sub.28).sub.3, amino radicals such as --N(R.sub.28).sub.2 ; acyl 
radicals such as --C(O)R.sub.28 ; acyloxy radicals such as --OC(O)R.sub.28 
; carbonyloxy radicals such as --COOR.sub.28 ; amido radicals such as 
--C(O)N(R.sub.28).sub.2 and --N(R.sub.28)COR.sub.28 ; sulfonyl radicals 
such as --SO.sub.2 R.sub.28 ; sulfinyl radicals such as 
--SO(R.sub.28).sub.2 ; thionyl radicals such as --SR.sub.28 ; phosphonyl 
radicals such as --P(O)(R.sub.28).sub.2 ; as well as halogen, nitro, 
cyano, trifluoromethyl and hydroxy radicals and the like, wherein each 
R.sub.28 can be a monovalent hydrocarbon radical such as alkyl, aryl, 
alkaryl, aralkyl and cycloalkyl radicals, with the provisos that in amino 
substituents such as --N(R.sub.28).sub.2, each R.sub.28 taken together can 
also compromise a divalent bridging group that forms a heterocyclic 
radical with the nitrogen atom, in amido substituents such as 
--C(O)N(R.sub.28).sub.2 and --N(R.sub.28)COR.sub.28, each R.sub.28 bonded 
to N can also be hydrogen, and in phosphonyl substituents such as 
--P(O)(R.sub.28).sub.2, one R.sub.28 can by hydrogen. It is to be 
understood that each R.sub.28 group in a particular substituent may be the 
same or different. Such hydrocarbon substituent radicals could possibly in 
turn be substituted with a permissible substituent such as already herein 
outlined above. 
Preferred alkylene oxides which can provide random or block oxyalkylene 
units in the complex hydrophobe compounds represented by formulae (i) and 
(ii) include alkylene oxides such as ethylene oxide, propylene oxide, 
1,2-butylene oxide, 2,3-butylene oxide, 1,2- and 2,3-pentylene oxide, 
cyclohexylene oxide, 1,2-hexylene oxide, 1,2-octylene oxide, 1,2-decylene 
oxide, and higher alpha-olefin epoxides; epoxidized fatty alcohols such as 
epoxidized soybean fatty alcohols and epoxidized linseed fatty alcohols; 
aromatic epoxides such as styrene oxide and 2-methylstyrene oxide; and 
hydroxy- and halogen-substituted alkylene oxides such as glycidol, 
epichlorohydrin and epibromohydrin. The preferred alkylene oxides are 
ethylene oxide and propylene oxide. Also included can be hydrocarbon 
residues from substituted and unsubstituted cyclic esters or ethers such 
as oxetane and tetrahydrofuran. It is understood that the compounds 
represented by formulae (i) and (ii) herein can contain random and/or 
block oxyalkylene units as well as mixtures of oxyalkylene units. It is 
further understood that each R.sub.4, R.sub.5, R.sub.10, R.sub.13 and 
R.sub.19 group in a particular substituent for all positive values of x, 
y, f, g and j respectively can be the same or different. 
The values of x, y, z, f, g and j are not narrowly critical and can vary 
over a wide range. For example, the values of x, y, z, f, g and j can 
range from 0 to about 200 or greater, preferably from about 0 to about 100 
or greater, and more preferably from about 0 to about 50 or greater. Any 
desired amount of alkylene oxide can be employed, for example, from 0 to 
about 90 weight percent or greater based on the weight of the complex 
hydrophobe compound. 
Referring to the general formulae (i) and (ii) above, it is appreciated 
that when R.sub.1, R.sub.2, R.sub.7 and/or R.sub.8 are a hydrocarbon 
residue of formulae (iii) above, the resulting compound may include any 
permissible number and combination of hydrophobic groups of the dendritic 
or cascading type. Such compounds included in the above general formulae 
should be easily ascertainable by one skilled in the art. Illustrative 
complex hydrophobe compounds having at least one active hydrogen useful in 
this invention and processes for preparation thereof are disclosed in 
copending U.S. patent application Ser. No. 07/887,648, which is 
incorporated herein by reference. 
In a preferred embodiment of this invention, the structure shown in formula 
(iii) can be a residue of the reaction product between epichlorohydrin and 
an alcohol, including those alcohols whose residues can be described by 
formula (iii), or a phenolic, or a mixture thereof. The structures which 
result can be described as complex hydrophobes of a dendritic or of a 
cascading nature. Pictorially, they can be described as shown below: 
##STR8## 
Preferred macromonomer compounds useful in this invention include those 
represented by the formulae: 
##STR9## 
wherein R.sup.1, R.sup.2, R.sup.4, R.sub.19, z and j are as defined 
herein. 
The macromonomer compounds useful in this invention can undergo further 
reaction(s) to afford desired derivatives thereof. Such permissible 
derivatization reactions can be carried out in accordance with 
conventional procedures known in the art. Illustrative derivatization 
reactions include, for example, esterification, etherification, 
alkoxylation, amination, alkylation, hydrogenation, dehydrogenation, 
reduction, acylation, condensation, carboxylation, oxidation, silylation 
and the like, including permissible combinations thereof. This invention 
is not intended to be limited in any manner by the permissible 
derivatization reactions or permissible derivatives of macromonomer 
compounds. 
More particularly, the hydroxyl-terminated macromonomer compounds of this 
invention can undergo any of the known reactions of hydroxyl groups 
illustrative of which are reactions with acyl halides to form esters; with 
ammonia, a nitrile, or hydrogen cyanide to form amines; with alkyl acid 
sulfates to form disulfates; with carboxylic acids and acid anhydrides to 
form esters and polyesters; with alkali metals to form salts; with ketenes 
to form esters; with acid anhydrides to form carboxylic acids; with oxygen 
to form aldehydes and carboxylic acids; ring-opening reactions with 
lactones, tetrahydrofuran; dehydrogenation to form aldehydes, isocyanates 
to form urethanes, and the like. 
The monoethylenically unsaturated macromonomer component is subject to 
considerably variation within the formula presented previously. The 
essence of the macromonomer is a complex hydrophobe carrying a 
polyethoxylate chain (which may include some polypropoxylate groups) and 
which is terminated with at least one hydroxy group. When the 
hydroxy-terminated polyethoxylate complex hydrophobe used herein is 
reacted with a monoethylenically unsaturated monoisocyanate, for example, 
the result is a monoethylenically unsaturated urethane in which a complex 
hydrophobe polyethoxylate structure is associated with a copolymerizable 
monoethylenic group via a urethane linkage. 
The monoethylenically unsaturated compound used to provide the 
monoethylenically unsaturated macromonomer is subject to wide variation. 
Any copolymerizable unsaturation may be employed, such as acrylate and 
methacrylate unsaturation. One may also use allylic unsaturation, as 
provided by allyl alcohol. These, preferably in the form of a 
hydroxy-functional derivative, as is obtained by reacting a C.sub.2 
-C.sub.4 monoepoxide, like ethylene oxide, propylene oxide or butylene 
oxide, with acrylic or methacrylic acid to form an hydroxy ester, are 
reacted in equimolar proportions with an organic compound, such as toluene 
diisocyanate or isophorone diisocyanate. The preferred monoethylenic 
monoisocyanate is styryl, as in alpha, alpha-dimethyl-m-isopropenyl benzyl 
isocyanate. Other suitable organic compounds include, for example, 
monoethylenically unsaturated esters, ethers, amides, ureas, anhydrides, 
other urethanes and the like. 
The polymers of this invention can be prepared via a variety of 
polymerization techniques known to those skilled in the art. 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 emulsion polymerization via 
batch, semi-continuous, or continuous processes, micellar polymerization, 
inverse emulsion polymerization, solution polymerization, non-aqueous 
dispersion polymerization, interfacial polymerization, emulsion 
polymerization, suspension polymerization, precipitation polymerization, 
addition polymerizations such as free radical, anionic, cationic or metal 
coordination methods, and the like. 
The thickeners of this invention possess structural attributes of two 
entirely different types of thickeners (those which thicken by 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. 
The aqueous emulsion copolymerization is entirely conventional. To obtain 
an estimate of thickening efficiency, the product can be diluted with 
water to about 1% solids content and then neutralized with alkali. The 
usual alkali is ammonium hydroxide, but sodium and potassium hydroxide, 
and even amines, like triethylamine, may be used for neutralization. The 
neutralized product dissolves in the water to provide an increase in the 
viscosity. In the normal mode of addition, the unneutralized thickener is 
added to a paint and then neutralized. This facilitates handling the 
thickener because it has a lower viscosity before neutralization. This 
procedure also makes more water available for the paint formulation. 
The polymers of this invention are preferably produced by conventional 
aqueous emulsion polymerization techniques, using appropriate emulsifiers 
for emulsifying the monomers and for maintaining the polymer obtained in a 
suitable, dispersed condition. Commonly used anionic surfactants such as 
sodium lauryl sulfate, dodecylbenzene sulfonate and ethoxylated fatty 
alcohol sulfate can be used as emulsifiers. The emulsifier may be used in 
a proportion of 1/2 to 6% of the weight monomers. 
Preferably, water-soluble initiators such as alkali metal or ammonium 
persulfate are used in amounts from 0.01 to 1.0% on the weight of 
monomers. A gradual addition thermal process employed at temperatures 
between 60.degree. C. to 100.degree. C. is preferred over redox systems. 
The polymerization system may contain small 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, and the like. The use of 
mercaptan modifier reduces the molecular weight of the polymer and 
therefore its thickening efficiency. 
The polymers of this invention may further be modified by introducing an 
amount of component (D), 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-(.alpha.-methylmethylenesulfonamide)-ethylene. 
The polymer may be utilized in a variety of ways to provide the thickener 
or thickened compositions of this invention. For example, the polymer, 
while in aqueous dispersion or dry form, may be blended into an aqueous 
system to be thickened followed by addition of a neutralizing agent. 
Alternatively, the polymer may first be neutralized in aqueous dispersion 
form and then blended with the aqueous system. Preferably, if 
co-thickening by a surfactant is desired, the components are separately 
blended (as dry components or as dispersions or slurries) into an aqueous 
dispersion to be thickened, followed by the neutralization step. Although 
aqueous concentrates of the polymer in acid form and the surfactant may be 
formed and added to an aqueous dispersion to be thickened as needed, 
followed by neutralization, such concentrates tend to be too viscous for 
easy handling. It is nevertheless possible to prepare either a dry blend 
or an aqueous, high solids composition which is sufficiently low in 
viscosity as to be pumpable or pourable, and then to further thicken the 
admixture by addition of an alkaline material. 
The polymer thickener may be provided in a dry state in number of ways. For 
example, the unneutralized polymer may be spray or drum dried and, if 
desired, blended with a surfactant co-thickener. However, it is also 
possible to spray dry or otherwise dehydrate the neutralized polymer 
thickener, and then reconstitute the aqueous thickener dispersion at a 
future time and place by agitation in a aqueous medium, provided the pH of 
the dispersion is maintained at pH 7 or higher. 
The more usual method of application of the dispersion of this invention 
for aqueous thickening is to add the aqueous dispersion of the polymer to 
the medium to be thickened and, after mixing, to introduce an alkaline 
material to neutralize the acid. The major portion of the thickening 
effect is obtained in a few minutes upon neutralization. In the presence 
of high concentrations of electrolytes, the viscosity development may take 
much longer. This method of applying a polymer to an aqueous system before 
neutralization enables one to handle a high solids thickener in a 
non-viscous state, to obtain uniform blend, and then to convert to a 
highly viscous condition by the simple addition of an alkaline material to 
bring the pH of the system to 7 or above. 
The aqueous solutions thickened with the neutralized polymers of this 
invention exhibit good viscosity stability even at a pH as high as 13. 
The polymer may be used to thicken compositions under acidic conditions in 
the presence of a relatively large amount of surfactants wherein the 
thickened composition, for example, an aqueous system, has a pH below 7, 
even as low as 1. 
An enhancement of thickening (herein termed "co-thickening") can result 
upon the addition of a surfactant to an aqueous system containing the 
polymer of this invention, when the polymer is neutralized. In some cases 
the thickening can be enhanced up to about 40 times the viscosity afforded 
by the neutralized polymer alone. A wide range of surfactants may be used. 
Although trace amounts of surfactant may be residually present from the 
polymerization of the monomers comprising the polymer (for example, 
whatever may remain of the about 1.5 weight percent surfactant on 
monomers), such amounts of surfactant are not believed to result in any 
measurable co-thickening. 
On the basis of an aqueous system containing about 0.1 to 5% by weight of 
polymer solids, a useful amount of surfactant for optimum co-thickening is 
about 0.1 to 1.0% by weight of the total system. As indicated, the amounts 
of polymer and surfactant co-thickener may vary widely, even outside these 
ranges, depending on polymer and surfactant type and other components of 
the aqueous system to be thickened. However, the co-thickening can reach a 
maximum as surfactant is added and then decreases as more surfactant is 
added. Hence, it may be uneconomical to employ surfactant in amounts 
outside the stated concentrations and polymer/surfactant ratios, but this 
can be determined in a routine manner in each case. 
The preferred method of application of the polymer and the surfactant for 
aqueous thickening is to add in any sequence the polymer and the 
surfactant to the medium to be thickened and, after mixing, to introduce 
an alkaline material to neutralize the acid. This method of applying 
polymer and surfactant to an aqueous system before neutralization enables 
one to handle a high solids thickener in a non-viscous state, to obtain a 
uniform blend, and then to convert to a highly viscous condition by the 
simple addition of an alkaline material to bring the pH of the system to 7 
or above. However, the polymer in the aqueous system may also be 
neutralized before addition of the surfactant. 
The surfactants which may be used include nonionics and anionics, singly or 
in combination, the selection necessarily depending upon compatibility 
with other ingredients of the thickened or thickenable dispersions of this 
invention. Cationic and amphoteric surfactants may also be used provided 
they are compatible with the polymer and other ingredients of the aqueous 
system, or are used in such small amounts as not to cause incompatibility. 
Suitable anionic surfactants that may be used include the higher fatty 
alcohol sulfates such as the sodium or potassium salt of the sulfates of 
alcohols having from 8 to 18 carbon atoms, alkali metal salts or amine 
salts of high fatty acid having 8 to 18 carbon atoms, and sulfonated alkyl 
aryl compounds such as sodium dodecyl benzene sulfonate. Examples of 
nonionic surfactants include alkylphenoxypolyethoxyethanols having alkyl 
groups of about 7 to 18 carbon atoms and about 9 to 40 or more oxyethylene 
units such as octylphenoxypolyethoxyethanols, 
dodecylphenoxypolyethoxyethanols; ethylene oxide derivatives of long-chain 
carboxylic acids, such as lauric, myristic, palmitic, oleic; ethylene 
oxide condensates of long-chain alcohols such as lauryl or cetyl alcohol, 
and the like. 
Examples of cationic surfactants include lauryl pyridinium chloride, 
octylbenzyltrimethylammonium chloride, dodecyltrimethylammonium chloride 
condensates of primary fatty amines and ethylene oxide, and the like. 
The foregoing and numerous other useful nonionic, anionic, cationic, and 
amphoteric surfactants are described in the literature, such as 
McCutcheon's Detergents & Emulsifiers 1981 Annual, North America Edition, 
MC Publishing Company, Glen Rock, N.J. 07452, U.S.A., incorporated herein 
by reference. 
In general, solvents and non-solvents (or mixtures of solvents, 
non-solvents, other organics and volatiles) can be used to manipulate the 
viscosity of polymer containing systems. In the examples herein, it is 
interesting to note how mineral spirits act like co-thickener, and how the 
water solubility of the other solvent influences how much mineral spirits 
can be added before the solution separates into a two phase system. The 
co-thickening 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 and 
improving the efficiency of the thickener. 
The amount of the polymer that may be dissolved in any given aqueous 
composition may fall within a wide range depending on the particular 
viscosity desired. 
Thus, although any effective amount of the polymer may be employed for 
dissolution, typically from about 0.05 to about 20%, preferably from about 
0.1 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 polymer is 
used. 
For latex paint compositions, the polymer may be dissolved therein in an 
amount of from about 0.05 to about 5%, and preferably from about 0.1 to 
about 3% by weight, based on the weight of the total composition including 
polymer. 
The polymers of this invention may be employed as thickeners for 
controlling viscosity of any aqueous based composition. An aqueous based 
composition is an aqueous composition as herein defined to be a 
composition wherein water comprises at least 10% by weight of the total 
composition (including 100% water). 
For example, aqueous dispersions, emulsions, suspensions, solutions, 
slurries and the like, may be thickened by the polymers of this invention. 
Typical aqueous compositions include compositions to be applied to textiles 
such as latex adhesives, warp sizes, backings for rugs and other pile 
fabrics. The polymer may also be used when thickening is desired in the 
purification of raw water such as the saline water used in the recovery of 
oil from exhausted oil wells by water flooding techniques. Other aqueous 
coatings compositions to which the polymer can be added for thickening 
purposes include drilling muds, caulks, adhesives, coating compositions 
such as paper coatings, furniture finishes, ink compositions, latex 
paints, foundary core washes, and the like. 
Preferably, the polymer 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 
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 typicaly include 
thickeners, antifoam agents, plasticizers, surfactants, coalescing agents, 
and the like. 
The polymers 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, dentrifrices, 
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 
and the like. 
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.