Polymers are disclosed which comprise: PA0 (A) about 1-99.9 weight percent of one or more alpha, beta-monoethylenically unsaturated carboxylic acids, typically methacrylic acids; PA0 (B) about 0-98.9 weight percent of one or more monoethylenically unsaturated monomers, typically ethyl acrylate; PA0 (C) about 0.1-99 weight percent of one or more monoethylenically unsaturated macromonomers, and PA0 (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.

RELATED APPLICATIONS 
The following are related, commonly assigned applications, filed on an even 
date herewith: 
U.S. patent application Ser. No. 07/887,645; U.S. patent application Ser. 
No. 07/887,646; U.S. patent application Ser. No. 07/887,642; U.S. patent 
application Ser. No. 07/887,673; U.S. patent application Ser. No. 
07/887,672; U.S. patent application Ser. No 07/887,641; U.S. patent 
application Ser. No. 07/887,648; U.S. patent application Ser. No. 
07/887,643; U.S. patent application Ser. No. 07/887,644; and U.S. patent 
application Ser. No. 07/887,671; all of which are incorporated herein by 
reference. 
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 rheology 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 
thererof. 
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 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 are 
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. 07/887,647, 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.sup.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.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. 
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.sup.7, R.sup.8, R.sub.11 and R.sup.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 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 .dbd.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 
copending U.S. patent application Ser. No. 07/887,647, 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 hydroxy-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 maromonomer 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 cothickener 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 anydrides 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 ingedients 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. 
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 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 300 milliliters 
of cyclohexane and 451.7 grams (2.05 mole) of nonylphenol. The solution 
was then heated to reflux and 58.9 grams (1.05 mole) of potassium 
hydroxide in 60 milliliters of water was slowly added via the addition 
funnel. After essentially all the water was recovered in the decanting 
head (60 milliliter+19 milliliters formed), the reaction was cooled to 
40.degree. C., and 92.5 grams (1.00 mole) of epichlorohydrin was slowly 
added. During the addition, the reaction temperature was maintained below 
60.degree. C. by controlling the rate of epichlorohydrin addition. After 
all the epichlorohydrin was added, the solution was allowed to stir for 
one hour, and then brought to reflux for an additional three hours. The 
reaction mixture was then filtered under vacuum through a steam-jacketed 
Buchner funnel to remove the potassium chloride formed as a by-product. 
The filtration process was performed a total of three times to remove the 
majority of the salts. 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 275 
grams of a pale-yellow liquid. End-group MW analysis gave a molecular 
weight of 459.7 (theoretical MW=496.8). Ir and nmr spectra were identical 
to previously recorded spectra for the compound. 
EXAMPLE 3 
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. 
EXAMPLE 4 
Preparation of Adduct of Nonylphenyl Glycidyl Ether and 5 Mole Ethoxylate 
of 1,3-Bis(nonylphenoxy)-2-propanol 
To a five neck, one liter, round bottom flask equipped as in Example 1 was 
added 119.8 grams (0.17 mole) of the 5 mole ethoxylate of 
1,3-bis(nonylphenoxy)-2-propanol and 100 milliliters of cyclohexane. The 
mixture was refluxed (100.degree. C.) for one hour to remove residual 
water, and then cooled to 50.degree. C. under nitrogen to add 0.5 grams of 
BF.sub.3 /Et.sub.2 O. Nonylphenyl glycidyl ether (46.0 grams, 0.17 mole) 
was then added to the flask over a one hour period, and the reaction was 
heated to reflux. After three hours at reflux, the reaction mixture was 
transferred to a separatory funnel, while hot, and washed with a saturated 
aqueous solution of sodium bicarbonate. The organic layer was separated 
from the water layer, and washed twice with hot deionized water. The 
washes were performed at 50.degree. C. to facilitate the separation of the 
two layers. The water and cyclohexane were then evaporated from the 
organic layer, under vacuum, to yield 145 grams of a pale-yellow, viscous 
liquid. End-group molecular weight analysis gave a molecular weight of 880 
(theoretical molecular weight=993). 
EXAMPLE 5 
Preparation of Poly(nonylphenol glycidyl ether) 
To a 500 milliliter round bottom equipped with an overhead stirrer, 
nitrogen inlet, reflux condenser, additional funnel, and temperature 
controller was charged 1.9 grams of ethanol (22 mmoles) and 200 grams of 
cyclohexane. The solution was brought to 50.degree. C. Once heated, 0.5 
milliliters (4 mmoles) of BF.sub.3 /Et.sub.2 O was added using a 2 
milliliter syringe. Once the acid was added, 100.0 grams of nonylphenol 
glycidyl ether (362 mmoles) was added dropwise so as to maintain a 
reaction temperature of 45.degree. C.-55.degree. C. Once the glycidyl 
ether was added, the solution is refluxed for 3 hours, then cooled to 
about 50.degree. C. 
While hot (&lt;60.degree. C.) the organic was transferred to a separatory 
funnel and was washed once with 100 milliliters of 5% sodium bicarbonate 
solution. The aqueous layer was drained and the organic was washed two 
more times with 100 milliliter portions of deionized water. The aqueous 
layers were decanted and the organic was dried for at least 1 hour over 
magnesium sulfate. Once dry the magnesium sulfate was filtered from the 
organic which was stripped of solvent using a rotary evaporator. The final 
yield of viscous polymer was 100 grams. The GPC molecular weight was 
Mw=2600 and the Mn=1700 based on monodisperse polystyrene standards. 
EXAMPLE 6 
Ethoxylation of Poly(nonylphenol glycidyl ether) 
To a 500 milliliter stainless steel Zipperclave was added 60.0 grams (0.035 
moles based on an approximate molecular weight of 1700 gram/mole) of the 
resin prepared in Example 5 along with 0.5 grams of potassium hydroxide. 
The vessel was attached to an automated ethoxylation unit and was heated 
to 50.degree. C. The vessel was continuously purged with nitrogen for 15 
minutes and was then heated to 100.degree. C. where it was again 
continuously purged with nitrogen for another 15 minutes. The vessel was 
then heated to 140.degree. C. and was given a series of 6 purges by 
pressuring the vessel up to 80 psi, and then venting. Once the venting 
process was complete, the vessel was pressured to 20 psi with nitrogen. 
The ethylene oxide lines were opened to the motor valves along with the 
main feed line on the Zipperclave. The feed was continued and the vessel 
pressure was regulated at 55 psi and a temperature of 140.degree. C. The 
automation was designed to hold the temperature and the pressure within 
safe operating limits while addition of ethylene oxide proceeded through a 
pair of motor control valves. The feed was allowed to continue until 60.0 
grams of ethylene oxide (1.362 moles) was added based on a difference 
weight of the feed cylinder. After the feed was complete, the reaction was 
allowed to continue for 1 hour after which the vessel was cooled to 
60.degree. C., purged 4 times with nitrogen to 80 psi and was dumped to a 
container. The final product yield was 115 grams with a theoretical yield 
of 120 grams. The GPC molecular weight of the product was Mw=3550 and the 
MN=2930 based on monodisperse polystyrene standards. 
EXAMPLE 7 
Preparation of Poly(phenyl glycidyl ether) 
To a 500 milliliter round bottom equipped with an overhead stirrer, 
nitrogen inlet, reflux condenser, addition funnel, and temperature 
controller was charged 47.06 grams of phenol (500 mmoles) and 100 grams of 
toluene. The solution was brought to 50.degree. C. Once heated, 1.0 
milliliter (8 mmoles) of BF.sub.3 /Et.sub.2 O was added using a 2 
milliliter syringe. Once the acid was added, 68.18 grams of phenyl 
glycidyl ether (454 mmoles) was added dropwise so as to maintain a 
reaction temperature of 45.degree. C.-55.degree. C. Once the glycidyl 
ether was added, the solution is refluxed for 3 hours, then cooled to 
about 50.degree. C. 
While hot (&lt;60.degree. C.) the organic was transferred to a separatory 
funnel and was washed once with 100 milliliters of 5% sodium bicarbonate 
solution. The aqueous layer was drained and the organic was washed two 
more times with 100 milliliter portions of deionized water. The aqueous 
layers were decanted and the organic was dried for at least 1 hour over 
magnesium sulfate. Once dry the magnesium sulfate was filtered from the 
organic which was stripped of solvent using a rotary evaporator. The final 
yield of viscous polymer was 90.3 grams (with 11% unreacted phenol). The 
GPC molecular weight was Mw=470 and the Mn=310 (on average a trimer) based 
on monodisperse polystyrene standards. 
EXAMPLE 8 
Preparation of 1,3-Bis(phenoxy)-2-propanol using the Cascading Polyol 
Technique 
To a 1 liter round bottom flask equipped with an overhead stirrer, nitrogen 
inlet, reflux condenser, addition funnel, and temperature controller was 
charged 94.11 grams of phenol (1 mole), 12.86 grams of tetraethylammonium 
iodide (0.05 moles), 3.00 grams of water (0.17 moles), 42.08 grams of 
potassium hydroxide (0.75 moles), and 250 grams of toluene. To a 100 
milliliter additional funnel was charged 23.13 grams of epichlorohydrin 
(0.25 moles) and 50 grams of toluene. The solution was brought to 
65.degree. C. at which time the epichlorohydrin solution was added over a 
period of 15 minutes while maintaining a reaction temperature of 
65.degree. C..+-.5.degree. C. The reaction was allowed to proceed for 48 
hours. 
After 48 hours, the solution was cooled down to room temperature. The 
toluene solution was washed with two 250 milliliters portions of deionized 
water. The aqueous layers were drained off, and the toluene was removed 
along with unreacted phenol using a rotary evaporator. The final yield of 
product was 64.5 grams which was 106% of theory (residual is phenol). 
Final product purity was about 95% as shown by GPC. 
EXAMPLE 9 
Dimerization of 1,3-Bis(phenoxy)-2-propanol using the Cascading Polyol 
Technique 
To a 250 milliliter round bottom flask equipped with an overhead stirrer, 
nitrogen inlet, reflux condenser, additional funnel, and temperature 
controller was charged 20.03 grams of 1,3-bis-(phenoxy)-2-propanol 
prepared in Example 8 (82 mmoles), 2.06 grams of tetraethylammonium iodide 
(8 mmoles), 0.49 grams of water (27 mmoles), 6.51 grams of potassium 
hydroxide (116 mmoles), and 125 grams of toluene. To a 100 milliliter 
addition funnel was charged 3.61 grams of epichlorohydrin (39 mmoles) and 
25 grams of toluene. The solution was brought to 65.degree. C. at which 
time the epichlorohydrin solution was added over a period of 15 minutes 
while maintaining a reaction temperature of 65.degree. C..+-.5.degree. C. 
The reaction was allowed to proceed for 48 hours. 
After 48 hours, the solution was cooled down to room temperature. The 
toluene solution was washed with two 250 milliliter portions of deionized 
water. The aqueous layers were drained off, and the toluene was removed 
using a rotary evaporator. The final yield of product was 21.6 grams which 
was 101% of theory. GPC showed two major components of the product. The 
first was the starting material at about 41% (Mn=220) and the second was 
the coupled product at about 59% (Mn=520). 
EXAMPLE 10 
Preparation of 1,3-Bis(hexadecyloxy)-2-propanol using the Cascading Polyol 
Technique 
To a 500 milliliter round bottom flask equipped with an overhead stirrer, 
nitrogen inlet, reflux condenser, additional funnel, and temperature 
controller was charged 60.61 grams of hexadecanol (0.25 moles), 6.18 grams 
of tetraethylammonium iodide (0.024 moles), 1.44 grams of water (0.082 
moles), 20.20 grams of potassium hydroxide (0.36 moles), and 125 grams of 
toluene. To a 100 milliliter addition funnel was charged 11.10 grams of 
epichlorohydrin (0.12 moles) and 25 grams of toluene. The solution was 
brought to 65.degree. C. at which time the epichlorohydrin solution was 
added over a period of 15 minutes while maintaining a reaction temperature 
of 65.degree. C..+-.5.degree. C. The reaction was allowed to proceed for 
48 hours. 
After 48 hours, the solution was cooled down to room temperature. The 
toluene solution was washed with two 250 milliliter portions of deionized 
water. The aqueous layers were drained off, and the toluene was removed 
using a rotary evaporator. The final yield of product was 70.9 grams which 
is 109% of theory (residual is hexadecanol). 
EXAMPLE 11 
Sulfation of 1,3-Bis(nonylphenoxy)-2-propanol-block-(propylene 
oxide).sub.10 -block-(ethylene oxide).sub.10 
To a 250 milliliter round bottom flask equipped with an overhead stirrer, a 
temperature controller, and a vacuum adapter was added 75.0 grams of the 
material from Example 13 (49 mmoles). The kettle was then evacuated to &lt;20 
mmHg and heated to 100.degree. C. to remove any water. After 1 hour, the 
kettle was cooled to 60.degree. C. while under vacuum. When reaching 
60.degree. C., vacuum was broken with nitrogen and 5.3 grams of sulfamic 
acid (54 mmoles) was added. After charging the sulfamic acid, the kettle 
was heated to 110.degree. C. and evacuated to &lt;20 mmHg. The reaction was 
allowed to proceed for 3 hours. 
At the end of the hold period, the kettle was cooled to 85.degree. C. and 
vacuum was broken with nitrogen. 1.2 grams of diethanolamine (11 mmoles) 
was slowly added under a blanket of nitrogen. This solution was stirred 
for 30 minutes. 10 grams of ethanol was added to the kettle and the 
temperature was regulated to 55.degree. C. This solution was stirred for 
30 minutes. The heat was removed from the kettle and 30 grams of water 
along with 20 grams of ethanol were added while maintaining good 
agitation. The solution was stirred for 15 minutes or until cooled to room 
temperature (&lt;35.degree. C.). 
The pH was checked by dissolving 2 grams of the product solution in 18 
grams of deionized water. If the pH was below 6.5, 0.2 gram increments of 
diethanolamine was added until the pH is between 6.5 and 7.5. 
EXAMPLE 12 
Preparation of 1,3-Bis(nonylphenoxy)-2-propanol-block-(propylene 
oxide).sub.10 
To a 500 milliliter stainless steel Zipperclave was added 100.0 grams 
(0.202 moles) of 1,3-bis(nonylphenoxy)-2-propanol prepared in Example 1 
along with 0.7 grams of potassium hydroxide. The vessel was attached to an 
automated unit and was heated to 50.degree. C. The vessel was continuously 
purged with nitrogen for 15 minutes and was then heated to 100.degree. C. 
where it was again continuously purged with nitrogen for another 15 
minutes. The vessel was then heated to 140.degree. C. and is given a 
series of 6 purges by pressuring the vessel up to 80 psi, and then 
venting. Once the venting process was completed, the vessel was pressured 
to 20 psi with nitrogen. 
Lines connected to a cylinder which had been precharged with 117.0 grams of 
propylene oxide (2.02 moles) were opened to the motor valves along with 
the main feed line on the Zipperclave. The feed was continued and the 
vessel pressure was regulated at 55 psi and a temperature of 140.degree. 
C. The automation was designed to hold the temperature and the pressure 
within safe operating limits while addition of ethylene oxide proceeded 
through a pair of motor control valves. The feed was allowed to continue 
until all of the propylene oxide had been fed. After the feed was 
complete, the reaction was allowed to continue for 1 hour after which the 
vessel was cooled to 60.degree. C., purged 4 times with nitrogen to 80 psi 
and was dumped to a container. The final product yield was 211 grams with 
a theoretical yield of 277 grams. The GPC molecular weight of the product 
was Mw=650 and the Mn=490 based on monodisperse polystyrene standards. 
EXAMPLE 13 
Preparation of 1,3-Bis(nonylphenoxy)-2-propanol-block-(propylene 
oxide).sub.10 -block-(ethylene oxide).sub.10 
To a 500 milliliter stainless steel Zipperclave was added 75.0 grams of the 
propoxylate prepared in Example 12 (0.070 moles) along with 0.3 grams of 
potassium hydroxide. The vessel was attached to an automated ethoxylation 
unit and was heated to 50.degree. C. The vessel was continuously purged 
with nitrogen for 15 minutes and was then heated to 100.degree. C. where 
it was again continuously purged with nitrogen for another 15 minutes. The 
vessel was then heated to 140.degree. C. and was given a series of 6 
purges by pressuring the vessel up to 80 psi, and then venting. Once the 
venting process was completed, the vessel was pressured to 20 psi with 
nitrogen. 
The ethylene oxide lines were opened to the motor valves along with the 
main feed line on the Zipperclave. The feed was continued and the vessel 
pressure was regulated at 55 psi and a temperature of 140.degree. C. The 
automation was designed to hold the temperature and the pressure within 
safe operating limits while addition of ethylene oxide proceeded through a 
pair of motor control valves. The feed was allowed to continue until 30.7 
grams ethylene oxide (0.696 moles) was added based on a difference weight 
of the feed cylinder. After the feed was complete, the reaction is allowed 
to continue for 1 hour after which the vessel was cooled to 60.degree. C., 
purged 4 times with nitrogen to 80 psi and was dumped to a container. The 
final product yield was 99 grams with a theoretical yield of 106 grams. 
EXAMPLE 14 
Preparation of Bis(nonylphenoxy) Adduct of 1,4-Butanediol Diglycidyl Ether 
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 506.8 grams (2.30 
mole) of nonylphenol and 350 milliliters of cyclohexane. The solution was 
heated to reflux, and 6.5 grams (1,3 weight percent based on nonylphenol) 
of potassium hydroxide in 15 milliliters of water was slowly added to the 
round bottom flask. After all the water was recovered in the decanting 
head (15 milliliters+2 milliliters formed), 220 grams (1.09 mole) of 
1,4-butanediol diglycidyl ether was added dropwise 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 710 grams of a pale-yellow liquid. 
Molecular weight by end-group MW analysis was 689.9 (theoretical 
MW=643.0). Ir and nmr spectra were consistent with the expected structure 
of the product. 
EXAMPLE 15 
Preparation of 3 Mole Ethoxylate of 1,3-Bis(nonylphenoxy)-2-propanol 
To a five hundred milliliter Zipperclave reactor were charged, under 
nitrogen, 200.1 grams (0.43 mole) of 1,3-bis(nonylphenoxy)-2-propanol 
prepared in Example 2 and 0.20 grams (0.1 weight percent) of BF.sub.3 
.multidot.Et.sub.2 O. The reaction mixture was heated to 80.degree. C., 
and 55.1 grams (1.25 mole) of ethylene oxide was fed to the reactor over a 
two hour period. After all the ethylene oxide was fed, the reaction 
mixture was allowed to cook out for one hour and then dumped hot, under 
nitrogen, into a jar containing 160 milliliters of a one percent aqueous 
solution of sodium hydroxide. The organic layer was separated from the 
water layer and washed twice with deionized water. The washes were 
performed at 90.degree. C. to facilitate the separation of the two layers. 
The product was then dried by azeotropic removal of the water, using 
cyclohexane (300 milliliters) as the entrainer. The cyclohexane was 
stripped off under vacuum to give a pale-yellow liquid with a molecular 
weight by end-group MW analysis of 601.7 (theoretical MW=629). Ir and nmr 
spectra were consistent with the expected structure of the product. 
EXAMPLE 16 
Preparation of 8 Mole Ethoxylate of Bis(nonylphenoxy) Adduct of 
1,4-Butanediol Diglycidyl Ether 
To a five hundred milliliter Zipperclave reactor were charged, under 
nitrogen, 150.2 grams (0.22 mole) of bis(nonylphenoxy) adduct of 
1,4-butanediol diglycidyl ether prepared in Example 14 and 0.30 grams (0.2 
weight percent) of BF.sub.3 .multidot.Et.sub.2 O. The reaction mixture was 
heated to 80.degree. C., and 77.5 grams (1.76 mole) of ethylene oxide was 
fed to the reactor over a two hour period. After all the ethylene oxide 
was fed, the reaction mixture was allowed to cook out for one hour and 
then dumped hot, under nitrogen, into a jar containing 160 milliliters of 
a one percent aqueous solution of sodium hydroxide. The organic layer was 
separated from the water layer and washed twice with deionized water. The 
washes were performed at 90.degree. C. to facilitate the separation of the 
two layers. The product was then dried by azeotropic removal of the water, 
using cyclohexane (300 milliliters) as the entrainer. The cyclohexane was 
stripped off under vacuum to give a pale-yellow liquid with a molecular 
weight by end-group MW analysis of 1047 (theoretical MW=995). Ir and nmr 
spectra were consistent with the expected structure of the product. 
EXAMPLE 17 
Preparation of Macromonomer Compound 
Into a 1 liter round bottom reaction flask equipped with a heating mantle, 
dean stark trap, condenser, thermometer, nitrogen bubbler, nitrogen purge 
line and stirrer was charged 300 grams of toluene and 63 grams of a 
surfactant identified as S-1 in Table A below. With nitrogen purge, the 
resulting solution was heated to reflux at approximately 110.degree. C. 
and azeotroped to remove trace water to dryness. The solution was 
subsequently cooled to 90.degree. C., and 1.5 grams of bismuth hex chem 
28% bismuth octoate catalyst (Mooney Chemical, Inc., Cleveland, Ohio) was 
charged and allowed to mix well, after which a stoichiometric amount of 
95% m-TMI aliphatic isocyanate (American Cyanamid, Stamford, Conn.) was 
charged. After the reaction proceeded at 90.degree. C. for 1.3 hours, the 
resulting product was cooled to 70.degree. C. and 0.03 grams of 
2,6-di-tert-4-methyl phenol (BHT) preservative was added. The mixture was 
poured into a stainless steel pan with large surface area to facilitate 
drying. The final product was a waxy material, and is designated herein as 
macromonomer M-1. 
TABLE A 
______________________________________ 
##STR10## 
R.sub.2 = hydrogen or a R.sub.3OCH.sub.2 residue. 
Moles of 
Surfactant 
R.sub.1 R.sub.2 /R.sub.3 
Ethoxylation 
______________________________________ 
S-1 Nonylphenol Hydrogen (R.sub.2) 
40 
S-2 Nonylphenol Nonylphenol (R.sub.3) 
40 
S-3 Nonylphenol Nonylphenol (R.sub.3) 
20 
S-4 Nonylphenol Octylphenol (R.sub.3) 
20 
S-5 Nonylphenol Octylphenol (R.sub.3) 
40 
S-6 Nonylphenol Nonylphenol (R.sub.3) 
80 
S-7 Nonylphenol Nonylphenol (R.sub.3) 
120 
______________________________________ 
EXAMPLES 18-34 
Preparation of Macromonomer Compounds 
In a manner similar to that described in Example 17, other macromonomers 
were prepared using stoichiometric amounts of the surfactants and 
unsaturated compounds identified in Table B below. 
TABLE B 
______________________________________ 
Example Unsaturated Macromonomer 
No. Surfactant 
Compound Designation 
______________________________________ 
18 S-2 m-TMI M-2 
19 S-3 m-TMI M-3 
20 S-4 m-TMI M-4 
21 S-5 m-TMI M-5 
22 S-6 m-TMI M-6 
23 S-7 m-TMI M-7 
24 S-2 Isocyanato Ethyl 
M-8 
Methacrylate 
25 S-5 Isocyanato Ethyl 
M-9 
Methacrylate 
26 S-1 Methacrylic Anhydride 
M-10 
27 S-2 Methacrylic Anhydride 
M-11 
28 S-5 Methacrylic Anhydride 
M-12 
29 S-6 Methacrylic Anhydride 
M-13 
30 S-2 Acrylic Anhydride 
M-14 
31 S-5 Acrylic Anhydride 
M-15 
32 S-6 Acrylic Anhydride 
M-16 
33 S-2 Crotonic Anhydride 
M-17 
34 S-5 Maleic Anhydride 
M-18 
______________________________________ 
EXAMPLE 35 
Preparation of Alkali Soluble Thickener 
A monomer mixture (300 grams) was prepared by charging ethyl acrylate 
(Aldrich), methacrylic acid (Aldrich), macromonomer M-1, 13 grams of a 75% 
solution of Aerosol.RTM. OT surfactant (American Cyanamid, Stamford, 
Conn.), and 3 grams of distilled deionized water to a bottle, and 
dispersing the contents with vigorous shaking. The ethyl acrylate, 
methacrylic acid and macromonomer M-1 were added in amounts identified in 
Table C below. A catalyst feed mixture comprised of 0.53 grams of sodium 
persulfate (Aldrich) and 52.47 grams of water was prepared in another 
container. To a 2 liter resin flask that had been immersed in a 
thermostated water bath and equipped with a 4-bladed stainless steel 
mechanical stirrer, Claisen connecting tube, water condenser, nitrogen 
sparge and bubble trap, thermometer and monomer and catalyst addition 
inlets, 1.20 grams of the sodium salt of vinyl sulfonic acid and 658.5 
grams of water were charged. The monomer mixture was charged to a 1-liter 
graduated monomer feed cylinder, and the catalyst solution was charged to 
a 125 milliliter graduated catalyst feed cylinder. Under nitrogen purge, 
the reactor was heated to 70.degree. C., whereupon 33 milliliters of the 
monomer mixture and 3 milliliters of the catalyst feed mixture were 
charged to the reaction vessel. The reaction vessel was subsequently 
heated to 80.degree. C. After allowing the monomers to react for 20 
minutes to form a seed product, the monomer and catalyst feed mixtures 
were conveyed to the reaction vessel by FMI pumps via 1/8" teflon tubing 
at a rate of 1.94 and 0.27 milliliters/minute, respectively, under 
continuous stirring at a reaction temperature held between 
76.degree.-82.degree. C. The reaction was allowed to proceed for another 
hour, after which the product was cooled and filtered with a 200 mesh 
nylon cloth. The coagulum was collected from the reaction vessel and 
filter cloth. Thickening ability of the resulting product was monitored by 
Brookfield viscosity at 6 rpm by diluting the 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. 
EXAMPLES 36-131 
Preparation of Alkali Soluble Thickeners 
In a manner similar to that described in Example 35, other alkali soluble 
thickeners were prepared using the monomers identified in Tables C-J below 
in the amounts identified in Tables C-J. Table C illustrates the influence 
of m-TMI-containing macromonomer concentration and ethoxylation on 
thickening efficiency. Table D illustrates the influence of mixing 
m-TMI-containing macromonomers of various ethoxylations on thickening 
efficiency. Table E illustrates the influence of unsaturation type of 
urethane-containing macromonomers on thickening efficiency. Table F 
illustrates the influence of macromonomer ester structure and ethoxylation 
on thickening efficiency. Table G illustrates the influence of acid type 
and concentration on thickening efficiency. Table H illustrates the 
influence of polymer glass transition temperature and water solubility on 
thickening efficiency. Table I illustrates the influence of cross-linkable 
monomer concentration on thickening efficiency. Table J illustrates the 
influence of mercaptan on thickening efficiency. As used in Tables C-J 
below, the following abbreviations have the indicated meanings: 
MM=Macromonomer; EA=Ethyl Acrylate; MAA=Methacrylic Acid; AA=Acrylic Acid; 
MA=Methyl Acrylate; t-BA=t-Butyl Acrylate; n-BA=n-Butyl Acrylate; 
MMA=Methyl Methacrylate; 2-EHP =2-Ethylhexyl Propionate Mercaptan; and 
2-HEA=2-Hydroxy Ethyl Acrylate. 
TABLE C 
__________________________________________________________________________ 
Thickener Composition by 
Brookfield Viscosity 
Weight (CPS) @ pH = 9.0 Thickener 
Example 
Macromonomer 
% MM 
% EA 
% MAA 
0.25% 
0.50% 0.75% Designation 
__________________________________________________________________________ 
35 M-1 10 50 40 90 380 1,000 P-1 
36 M-2 5 55 40 270 11,400 103,600 P-2 
37 M-2 10 50 40 120 3,100 60,000 P-3 
38 M-2 10 50 40 105 10,400 130,000 P-3a 
39 M-2 20 40 40 25 2,150 50,500 P-4 
40 M-2 30 30 40 10 790 20,000 P-5 
41 M-3 5 55 40 390 2,260 17,900 P-6 
42 M-3 6.5 53.5 
40 142 1,200 18,500 P-7 
43 M-3 10 50 40 220 3,050 40,000 P-8 
44 M-3 20 40 40 75 2,350 27,500 P-9 
45 M-4 10 50 40 242 4,400 39,000 P-10 
46 M-5 10 50 40 45 7,400 84,000 P-11 
47 M-5 20 40 40 34 4,450 59,000 P-12 
48 M-6 5 55 40 460 25,500 88,000 P-13 
49 M-6 10 50 40 105 39,000 150,000 P-14 
50 M-6 15 45 40 195 43,000 140,000 P-15 
51 M-6 20 40 40 125 52,500 187,000 P-16 
52 M-6 30 30 40 315 56,500 162,000 P-17 
53 M-7 5 55 40 230 7,800 15,800 P-18 
54 M-7 10 50 40 900 17,400 35,000 P-19 
__________________________________________________________________________ 
TABLE D 
__________________________________________________________________________ 
Thickener Composition by 
Brookfield Viscosity 
Weight (CPS) @ pH = 9.0 Thickener 
Example 
Macromonomer 
% MM 
% EA 
% MAA 
0.25% 
0.50% 0.75% Designation 
__________________________________________________________________________ 
55 M-3:M-6 10 50 40 225 24,000 85,000 P-20 
1:1 
56 M-2:M-6 10 50 40 135 21,200 134,000 P-21 
1:1 
__________________________________________________________________________ 
TABLE E 
__________________________________________________________________________ 
Thickener Composition by 
Brookfield Viscosity 
Weight (CPS) @ pH = 9.0 Thickener 
Example 
Macromonomer 
% MM 
% EA 
% MAA 
0.25% 
0.50% 0.75% Designation 
__________________________________________________________________________ 
57 M-8 5 55 40 250 14,800 124,000 P-22 
58 M-8 10 50 40 93 11,200 125,400 P-23 
59 M-8 20 40 40 45 6,140 84,500 P-24 
60 M-9 5 55 40 275 6,200 57,000 P-25 
61 M-9 10 50 40 250 10,100 80,000 P-26 
62 M-9 20 40 40 90 7,800 90,000 P-27 
63 M-9 30 30 40 45 5,200 69,000 P-28 
__________________________________________________________________________ 
TABLE F 
__________________________________________________________________________ 
Thickener Composition by 
Brookfield Viscosity 
Weight (CPS) @ pH = 9.0 Thickener 
Example 
Macromonomer 
% MM 
% EA 
% MAA 
0.25% 0.50% 0.75% Designation 
__________________________________________________________________________ 
64 M-10 10 50 40 130 285 410 P-29 
65 M-11 10 50 40 190 19,500 152,000 P-30 
66 M-11 20 40 40 120 13,500 146,000 P-31 
67 M-11 30 30 40 96 8,000 73,000 P-32 
68 M-12 5 55 40 260 5,400 51,000 P-33 
69 M-12 10 50 40 175 9,200 71,000 P-34 
70 M-12 20 40 40 100 7,400 77,000 P-35 
71 M-12 30 30 40 62 4,500 63,000 P-36 
72 M-13 5 55 40 320 25,600 79,000 P-37 
73 M-13 10 50 40 97 28,000 125,000 P-38 
74 M-13 20 40 40 300 58,200 171,000 P-39 
75 M-13 30 30 40 730 63,000 163,000 P-40 
76 M-14 10 50 40 410 22,700 130,000 P-41 
77 M-14 20 40 40 1225 44,500 168,000 P-42 
78 M-14 30 30 40 1010 42,500 180,000 P-43 
79 M-15 5 55 40 84 1,680 29,000 P-44 
80 M-15 10 50 40 350 12,000 83,000 P-45 
81 M-15 20 40 40 220 24,500 122,000 P-46 
82 M-15 30 30 40 1050 33,000 133,000 P-47 
83 M-16 5 55 40 450 17,720 45,300 P-48 
84 M-16 10 50 40 1,345 27,000 98,000 P-49 
85 M-16 20 40 40 3,450 65,800 158,000 P-50 
86 M-16 30 30 40 11,600 81,000 157,000 P-51 
87 M-17 10 50 40 410 12,000 60,000 P-52 
88 M-17 20 40 40 255 10,600 46,300 P-53 
89 M-17 30 30 40 38 2,525 13,500 P-54 
90 M-18 5 55 40 100 810 3,500 P-55 
91 M-18 10 50 40 110 1,420 5,940 P-56 
92 M-18 20 40 40 30 870 2,425 P-57 
__________________________________________________________________________ 
TABLE G 
__________________________________________________________________________ 
Thickener Composition by 
Brookfield Viscosity 
Weight (CPS) @ pH = 9.0 Thickener 
Example 
Macromonomer 
% MM 
% EA 
% MAA 
% AA 
0.25% 
0.50% 0.75% Designation 
__________________________________________________________________________ 
93 M-2 10 60 30 0 1520 12,200 102,000 P-58 
94 M-2 10 70 20 0 45 3,800 50,000 P-59 
95 M-2 10 80 10 0 &lt;10 &lt;10 &lt;10 P-60 
96 M-2 10 60 0 30 &lt;10 95 6,800 P-61 
97 M-6 20 60 20 0 15 13,500 43,500 P-62 
98 M-6 5 65 30 0 210 13,000 56,500 P-63 
99 M-6 10 60 30 0 77 24,000 88,000 P-64 
100 M-6 20 50 30 0 17 7,600 79,000 P-65 
101 M-6 5 45 50 0 130 7,060 28,000 P-66 
102 M-6 10 40 50 0 86 16,700 52,500 P-67 
103 M-6 20 30 50 0 130 28,000 122,000 P-68 
104 M-11 10 70 0 20 &lt;10 213 7300 P-69 
105 M-17 10 50 20 20 710 16,500 66,000 P-70 
__________________________________________________________________________ 
TABLE H 
__________________________________________________________________________ 
Thickener Composition by 
Brookfield Viscosity 
Weight (CPS) @ pH = 9.0 Thickener 
Example 
Macromonomer 
% MM 
% EA 
% MAA 
% Other 
0.25% 
0.50% 0.75% Designation 
__________________________________________________________________________ 
106 M-2 10 40 40 10 90 5,760 82,000 P-71 
MMA 
107 M-2 10 30 40 20 15 1,125 55,000 P-72 
MMA 
108 M-2 10 20 40 30 10 207 6,000 P-73 
MMA 
109 M-2 10 0 40 50 &lt;10 &lt;10 &lt;10 P-74 
MMA 
110 M-2 10 30 40 20 20 310 1,330 P-75 
styrene 
111 M-2 10 40 40 10 95 7,540 75,500 P-76 
styrene 
112 M-2 10 40 40 10 220 13,800 118,000 P-77 
n-BA 
113 M-2 10 30 40 20 185 7,400 66,500 P-78 
n-BA 
114 M-2 10 40 40 10 130 10,100 100,000 P-79 
t-BA 
115 M-2 10 30 40 20 125 7,200 77,500 P-80 
t-BA 
116 M-2 10 40 40 10 100 6,900 121,000 P-81 
MA 
117 M-2 10 30 40 20 73 5,000 90,000 P-82 
MA 
118 M-6 20 30 40 10 33 15,400 150,000 P-83 
MMA 
__________________________________________________________________________ 
TABLE I 
__________________________________________________________________________ 
Thickener Composition by 
Brookfield Viscosity 
Weight (CPS) @ pH = 9.0 Thickener 
Example 
Macromonomer 
% MM 
% EA 
% MAA 
%2-HEA 
0.25% 
0.50% 0.75% Designation 
__________________________________________________________________________ 
119 M-2 10 47.7 
40 2.3 97 9,060 127,000 P-84 
120 M-2 10 57.7 
30 2.3 62 6,300 76,000 P-85 
121 M-2 20 37.5 
40 2.5 27 6,200 116,600 P-86 
122 M-2 20 35 40 5 &lt;10 260 18,600 P-87 
123 M-2 20 32.5 
40 7.5 20 720 40,000 P-88 
124 M-2 20 30 40 10 10 520 29,500 P-89 
__________________________________________________________________________ 
TABLE J 
__________________________________________________________________________ 
Thickener Composition by 
Brookfield Viscosity 
Weight (CPS) @ pH = 9.0 Thickener 
Example 
Macromonomer 
% MM % EA 
% MAA %2-HEP* 
0.25% 0.50% 0.75% Designation 
__________________________________________________________________________ 
125 M-2 10 40 50 .05 165 22,800 142,000 P-90 
126 M-2 10 50 40 0.2 18 2,060 66,500 P-91 
127 M-2 10 50 40 0.3 &lt;10 115 9,700 P-92 
128 M-2 10 50 40 0.5 &lt;10 12 355 P-93 
129 M-2 10 50 40 1 &lt;10 &lt;10 &lt;10 P-94 
130 M-6 10 50 40 .05 230 23,700 90,700 P-95 
131 M-6 10 50 40 .2 30 5,170 33,000 P-96 
__________________________________________________________________________ 
*% charged to reactor based on monomer. 
EXAMPLES 132-187 
Co-Thickening with Surfactants 
The addition of certain surfactants to an associative polymer solution 
produces a co-thickening effect. The results in Table L below show the 
co-thickening effect produced by the addition with thorough mixing of 
certain surfactants identified in Table K below in the amounts identified 
in Table L to a 0.5% alkaline solution of an alkali soluble thickener 
identified in Table L as measured with a Brookfield Viscometer at 6 rpm at 
pH=9.0. 
TABLE K 
______________________________________ 
##STR11## 
R.sub.2 = hydrogen or a R.sub.3OCH.sub.2 residue. 
Moles of 
Surfactant 
R.sub.1 R.sub.2 /R.sub.3 
Ethoxylation 
______________________________________ 
S-8 Nonylphenol Nonylphenol (R.sub.3) 
20 
S-9 Nonylphenol Nonylphenol (R.sub.3) 
40 
S-10 Nonylphenol Nonylphenol (R.sub.3) 
80 
S-11 Nonylphenol Hydrogen (R.sub.2) 
25 
S-12 Nonylphenol Hydrogen (R.sub.2) 
40 
S-13 Nonylphenol Octylphenol (R.sub.3) 
20 
S-14 Nonylphenol Octylphenol (R.sub.3) 
40 
S-15* Nonylphenol Nonylphenol (R.sub.3) 
40 
S-16 Octylphenol Hydrogen (R.sub.2) 
25 
______________________________________ 
*Sulfated derivative. 
TABLE L 
______________________________________ 
Surfactant Brookfield 
Exam- Concentration 
Thick- 
Viscosity 
ple Surfactant 
(wt. %) ener (cps) @ pH = 9.0 
______________________________________ 
132 S-8 0.0 P-3 3100 
S-8 0.2 P-3 32700 
S-8 0.4 P-3 45700 
S-8 0.8 P-3 63300 
S-8 1.0 P-3 65500 
S-8 2.0 P-3 &gt;100000 
133 S-9 0.2 P-3 24200 
S-9 0.4 P-3 18700 
S-9 0.8 P-3 6600 
S-9 1.0 P-3 4060 
2.0 P-3 1225 
134 S-10 0.2 P-3 20600 
S-10 0.4 P-3 17300 
S-10 0.8 P-3 8500 
S-10 1.0 P-3 6300 
S-10 2.0 P-3 1850 
135 S-11 0.2 P-3 12000 
S-11 0.4 P-3 3160 
S-11 0.8 P-3 700 
S-11 1.0 P-3 485 
S-11 2.0 P-3 480 
136 S-12 0.2 P-3 9200 
S-12 0.4 P-3 4500 
S-12 0.8 P-3 1000 
S-12 1.0 P-3 875 
S-12 2.0 P-3 565 
137 S-13 0.2 P-3 34300 
S-13 0.4 P-3 26700 
S-13 0.8 P-3 11500 
S-13 1.0 P-3 8600 
S-13 2.0 P-3 2450 
138 S-14 0.2 P-3 22200 
S-14 0.4 P-3 17200 
S-14 0.8 P-3 6900 
S-14 1.0 P-3 4500 
S-14 2.0 P-3 1500 
139 S-15 0.2 P-3 10500 
S-15 0.4 P-3 4940 
S-15 0.8 P-3 2160 
S-15 1.0 P-3 1450 
S-15 2.0 P-3 355 
140 S-16 0.2 P-3 14300 
S-16 0.4 P-3 4080 
S-16 0.8 P-3 1075 
S-16 1.0 P-3 735 
S-16 2.0 P-3 485 
141 S-8 0.0 P-2 11400 
S-8 0.2 P-2 23500 
S-8 0.4 P-2 34000 
S-8 0.8 P-2 64000 
S-8 1.0 P-2 71000 
S-8 2.0 P-2 93000 
142 S-9 0.2 P-2 11000 
S-9 0.4 P-2 4000 
S-9 0.8 P-2 2000 
S-9 1.0 P-2 1400 
S-9 2.0 P-2 850 
143 S-10 0.2 P-2 10500 
S-10 0.4 P-2 5000 
S-10 0.8 P-2 2000 
S-10 1.0 P-2 1600 
S-10 2.0 P-2 950 
144 S-11 0.2 P-2 2700 
S-11 0.4 P-2 1000 
S-11 0.8 P-2 800 
S-11 1.0 P-2 660 
S-11 2.0 P-2 620 
145 S-12 0.2 P-2 2800 
S-12 0.4 P-2 1000 
S-12 0.8 P-2 850 
S-12 1.0 P-2 660 
S-12 2.0 P-2 650 
146 S-8 0.0 P-4 2150 
S-8 0.2 P-4 19000 
S-8 0.4 P-4 31000 
S-8 0.8 P-4 55000 
S-8 1.0 P-4 61000 
S-8 2.0 P-4 85000 
147 S-9 0.2 P-4 19500 
S-9 0.4 P-4 21500 
S-9 0.8 P-4 11500 
S-9 1.0 P-4 7400 
S-9 2.0 P-4 2250 
148 S-10 0.2 P-4 12600 
S-10 0.4 P-4 17400 
S-10 0.8 P-4 12600 
S-10 1.0 P-4 6600 
S-10 2.0 P-4 2600 
149 S-11 0.2 P-4 17400 
S-11 0.4 P-4 7800 
S-11 0.8 P-4 1650 
S-11 1.0 P-4 860 
S-11 2.0 P-4 560 
150 S-12 0.2 P-4 14600 
S-12 0.4 P-4 7800 
S-12 0.8 P-4 1500 
S-12 1.0 P-4 960 
S-12 2.0 P-4 450 
151 S-8 0.0 P-5 790 
S-8 0.2 P-5 4600 
S-8 0.4 P-5 19600 
S-8 0.8 P-5 42000 
S-8 1.0 P-5 50000 
S-8 2.0 P-5 90000 
152 S-9 0.2 P-5 5800 
S-9 0.4 P-5 13200 
S-9 0.8 P-5 9200 
S-9 1.0 P-5 5200 
S-9 2.0 P-5 1600 
153 S-10 0.2 P-5 4050 
S-10 0.4 P-5 10400 
S-10 0.8 P-5 9400 
S-10 1.0 P-5 5000 
S-10 2.0 P-5 1600 
154 S-11 0.2 P-5 10600 
S-11 0.4 P-5 4200 
S-11 0.8 P-5 1400 
S-11 1.0 P-5 970 
S-11 2.0 P-5 410 
155 S-12 0.2 P-5 6000 
S-12 0.4 P-5 4200 
S-12 0.8 P-5 1150 
S-12 1.0 P-5 600 
S-12 2.0 P-5 340 
156 S-8 0.0 P-7 1200 
S-8 0.2 P-7 9000 
S-8 0.4 P-7 21000 
S-8 0.8 P-7 37000 
S-8 1.0 P-7 49000 
S-8 2.0 P-7 78000 
157 S-9 0.2 P-7 1600 
S-9 0.4 P-7 1350 
S-9 0.8 P-7 900 
S-9 1.0 P-7 762 
S-9 2.0 P-7 565 
158 S-10 0.2 P-7 1100 
S-10 0.4 P-7 1150 
S-10 0.8 P-7 900 
S-10 1.0 P-7 823 
S-10 2.0 P-7 650 
159 S-11 0.2 P-7 1175 
S-11 0.4 P-7 685 
S-11 0.8 P-7 503 
S-11 1.0 P-7 495 
S-11 2.0 P-7 502 
160 S-12 0.2 P-7 950 
S-12 0.4 P-7 675 
S-12 0.8 P-7 525 
S-12 1.0 P-7 500 
S-12 2.0 P-7 480 
161 S-8 0.0 P-13 25500 
S-8 0.2 P-13 31500 
S-8 0.4 P-13 46500 
S-8 0.8 P-13 60000 
S-8 1.0 P-13 60000 
S-8 2.0 P-13 62500 
162 S-9 0.2 P-13 8640 
S-9 0.4 P-13 2940 
S-9 0.8 P-13 1200 
S-9 1.0 P-13 1000 
S-9 2.0 P-13 750 
163 S-10 0.2 P-13 10100 
S-10 0.4 P-13 4200 
S-10 0.8 P-13 1450 
S-10 1.0 P-13 1300 
S-10 2.0 P-13 900 
164 S-12 0.2 P-13 2540 
S-12 0.4 P-13 1125 
S-12 0.8 P-13 750 
S-12 1.0 P-13 670 
S-12 2.0 P-13 610 
165 S-8 0.0 P-14 39000 
S-8 0.2 P-14 61000 
S-8 0.4 P-14 73500 
S-8 0.8 P-14 87000 
S-8 1.0 P-14 93500 
S-8 2.0 P-14 122000 
166 S-9 0.2 P-14 41000 
S-9 0.4 P-14 13700 
S-9 0.8 P-14 6200 
S-9 1.0 P-14 3500 
S-9 2.0 P-14 1200 
167 S-10 0.2 P-14 38200 
S-10 0.4 P-14 20500 
S-10 0.8 P-14 7300 
S-10 1.0 P-14 5400 
S-10 2.0 P-14 1950 
168 S-12 0.2 P-14 13000 
S-12 0.4 P-14 4300 
S-12 0.8 P-14 975 
S-12 1.0 P-14 950 
S-12 2.0 P-14 660 
169 S-8 0.0 P-16 52500 
S-8 0.2 P-16 95000 
S-8 0.4 P-16 92000 
S-8 0.8 P-16 122000 
S-8 1.0 P-16 125000 
S-8 2.0 P-16 138000 
170 PS-9 0.2 P-16 73500 
PS-9 0.4 P-16 53000 
PS-9 0.8 P-16 25000 
PS-9 1.0 P-16 21000 
PS-9 2.0 P-16 5400 
171 S-10 0.2 P-16 52800 
S-10 0.4 P-16 34500 
S-10 0.8 P-16 5400 
S-10 1.0 P-16 2925 
S-10 2.0 P-16 775 
172 S-13 0.2 P-16 45800 
S-13 0.4 P-16 54000 
S-13 0.8 P-16 50800 
S-13 1.0 P-16 54500 
S-13 2.0 P-16 63000 
173 S-14 0.2 P-16 22700 
S-14 0.4 P-16 2480 
S-14 0.8 P-16 710 
S-14 1.0 P-16 532 
S-14 2.0 P-16 415 
174 S-8 0.0 P-29 285 
S-8 0.2 P-29 285 
S-8 0.4 P-29 360 
S-8 0.8 P-29 477 
S-8 1.0 P-29 505 
S-8 2.0 P-29 837 
175 S-9 0.2 P-29 282 
S-9 0.4 P-29 285 
S-9 0.8 P-29 284 
S-9 1.0 P-29 298 
S-9 2.0 P-29 322 
176 S-10 0.2 P-29 272 
S-10 0.4 P-29 278 
S-10 0.8 P-29 285 
S-10 1.0 P-29 297 
S-10 2.0 P-29 315 
177 S-12 0.2 P-29 267 
S-12 0.4 P-29 279 
S-12 0.8 P-29 298 
S-12 1.0 P-29 311 
S-12 2.0 P-29 320 
178 S-8 0.0 P-30 19500 
S-8 0.2 P-30 79000 
S-8 0.4 P-30 71200 
S-8 0.8 P-30 81000 
S-8 1.0 P-30 89500 
S-8 2.0 P-30 175000 
179 S-9 0.2 P-30 52000 
S-9 0.4 P-30 35500 
S-9 0.8 P-30 16500 
S-9 1.0 P-30 15600 
S-9 2.0 P-30 5620 
180 S-10 0.2 P-30 47200 
S-10 0.4 P-30 26300 
S-10 0.8 P-30 20300 
S-10 1.0 P-30 13400 
S-10 2.0 P-30 4700 
181 S-12 0.2 P-30 23000 
S-12 0.4 P-30 6840 
S-12 0.8 P-30 3125 
S-12 1.0 P-30 1750 
S-12 2.0 P-30 1225 
182 S-8 0.0 P-46 24500 
S-8 0.2 P-46 79000 
S-8 0.4 P-46 75000 
S-8 0.8 P-46 86000 
S-8 1.0 P-46 95000 
S-8 2.0 P-46 150000 
183 S-9 0.2 P-46 40500 
S-9 0.4 P-46 31000 
S-9 0.8 P-46 15300 
S-9 1.0 P-46 9400 
S-9 2.0 P-46 2300 
184 S-11 0.2 P-46 20000 
S-11 0.4 P-46 7300 
S-11 0.8 P-46 1350 
S-11 1.0 P-46 900 
S-11 2.0 P-46 380 
185 S-13 0.2 P-46 63500 
S-13 0.4 P-46 42000 
S-13 0.8 P-46 23000 
S-13 1.0 P-46 16000 
S-13 2.0 P-46 4850 
186 S-14 0.2 P-46 36000 
S-14 0.4 P-46 25000 
S-14 0.8 P-46 11000 
S-14 1.0 P-46 9300 
S-14 2.0 P-46 1900 
187 S-16 0.2 P-46 19000 
S-16 0.4 P-46 9300 
S-16 0.8 P-46 1250 
S-16 1.0 P-46 750 
S-16 2.0 P-46 290 
______________________________________ 
EXAMPLES 188-232 
Co-Thickening with Surfactants 
The degree of ethoxylation of a surfactant added to an associative polymer 
solution influences the co-thickening effect. The results in Table N below 
show the co-thickening effect produced by the addition with thorough 
mixing of certain surfactants identified in Table M below in the amounts 
identified in Table N to a 0.3% (Examples 172-189) , 0.5% (Examples 
190-215) or 0.75% (Example 216) alkaline solution of an alkali soluble 
thickener identified in Table N as measured with a Brookfield Viscometer 
at 6 rpm at pH=9.0. 
##STR12## 
R.sub.2 =hydrogen or a R.sub.3 --O--CH.sub.2 -- residue. 
TABLE M 
______________________________________ 
Moles of 
Surfactant 
R.sub.1 R.sub.2 /R.sub.3 
Ethoxylation 
______________________________________ 
S-17 Nonylphenol Hydrogen (R.sub.2) 
4 
S-18 Nonylphenol Hydrogen (R.sub.2) 
6 
S-19 Nonylphenol Hydrogen (R.sub.2) 
7 
S-20 Nonylphenol Hydrogen (R.sub.2) 
8 
S-21 Nonylphenol Hydrogen (R.sub.2) 
9 
S-22 Nonylphenol Hydrogen (R.sub.2) 
10 
S-23 Nonylphenol Hydrogen (R.sub.2) 
15 
S-24 Nonylphenol Hydrogen (R.sub.2) 
25 
S-25 Nonylphenol Hydrogen (R.sub.2) 
40 
S-26 Octylphenol Hydrogen (R.sub.2) 
1 
S-27 Octylphenol Hydrogen (R.sub.2) 
3 
S-28 Octylphenol Hydrogen (R.sub.2) 
5 
S-29 Octylphenol Hydrogen (R.sub.2) 
7 
S-30 Octylphenol Hydrogen (R.sub.2) 
9 
S-31 Octylphenol Hydrogen (R.sub.2) 
12 
S-32 Octylphenol Hydrogen (R.sub.2) 
16 
S-33 C11-C15 Secondary 
Hydrogen (R.sub.2) 
5 
Alcohol 
S-34 C11-C15 Secondary 
Hydrogen (R.sub.2) 
9 
Alcohol 
______________________________________ 
TABLE N 
______________________________________ 
Surfactant Brookfield 
Exam- Concentration 
Thick- 
Viscosity 
ple Surfactant 
(wt. %) ener (cps) @ pH = 9.0 
______________________________________ 
188 S-17 0.8 P-1 890 
189 S-18 0.8 P-1 1340 
190 S-19 0.8 P-1 630 
191 S-20 0.8 P-1 205 
192 S-21 0.8 P-1 143 
193 S-22 0.8 P-1 113 
194 S-23 0.8 P-1 85 
195 S-24 0.8 P-1 57 
196 S-25 0.8 P-1 68 
197 S-17 0.8 P-3 17800 
198 S-18 0.8 P-3 35800 
199 S-19 0.8 P-3 21300 
200 S-20 0.8 P-3 820 
201 S-21 0.8 P-3 230 
202 S-22 0.8 P-3 147 
203 S-23 0.8 P-3 118 
204 S-24 0.8 P-3 82 
205 S-25 0.8 P-3 77 
206 S-17 0.8 P-42 57000 
207 S-18 0.8 P-42 134000 
208 S-19 0.8 P-42 112000 
209 S-21 0.8 P-42 2450 
210 S-22 0.8 P-42 800 
211 S-23 0.8 P-42 3250 
212 S-26 0.8 P-42 43000 
213 S-27 0.8 P-42 37000 
214 S-28 0.8 P-42 71000 
215 S-29 0.8 P-42 5800 
216 S-30 0.8 P-42 375 
217 S-31 0.8 P-42 650 
218 S-32 0.8 P-42 2400 
219 S-17 0.8 P-46 68000 
220 S-18 0.8 P-46 13000 
221 S-19 0.8 P-46 88000 
222 S-21 0.8 P-46 2900 
223 S-22 0.8 P-46 1400 
224 S-23 0.8 P-46 2400 
225 S-26 0.8 P-46 25000 
226 S-27 0.8 P-46 38500 
227 S-28 0.8 P-46 77000 
228 S-29 0.8 P-46 7200 
229 S-30 0.8 P-46 550 
230 S-31 0.8 P-46 690 
231 S-32 0.8 P-46 1775 
232 Aerosol .RTM. 
0.0 P-4 50500 
OT 
Aerosol .RTM. 
0.1 P-4 93500 
OT 
Aerosol .RTM. 
0.2 P-4 42000 
OT 
Aerosol .RTM. 
0.4 P-4 11200 
OT 
Aerosol .RTM. 
0.8 P-4 3700 
OT 
Aerosol .RTM. 
1.0 P-4 7200 
OT 
Aerosol .RTM. 
2.0 P-4 10600 
OT 
______________________________________ 
EXAMPLES 233-245 
Co-Thickening with Solvents and Non-Solvents 
Solvents and non-solvents added to an associative polymer solution 
influences the co-thickening effect. The results in Table P below show the 
co-thickening effect produced by the addition with thorough mixing of 
certain solvents and non-solvents identified in Table O below in the 
amounts identified in Table P to a 0.75% alkaline solution of an alkali 
soluble thickener identified in Table P as measured with a Brookfield 
Viscometer at 6 rpm at pH=9.0. 
TABLE O 
______________________________________ 
Solvent 
Designation Solvent 
______________________________________ 
O-1 mineral spirits 
O-2 butanol 
O-3 Isobutanol 
O-4 Isopropanol 
O-5 2-Ethylhexanol 
O-6 Butyl Carbitol 
O-7 Butyl DiPropasol 
O-8 Butyl Propasol 
O-9 Propyl DiPropasol 
O-10 Propyl Propasol 
O-11 Methyl DiPropasol 
O-12 Methyl Propasol 
______________________________________ 
TABLE P 
__________________________________________________________________________ 
Solvent Solvent 0-1 
Brookfield 
Concentration 
Concentration 
Viscosity 
Example 
Thickener 
Solvent 
(wt. %) (wt. %) (cps) @ pH = 9.0 
__________________________________________________________________________ 
233 P-3 0-6 5 0 29200 
P-3 0-6 10 0 865 
P-3 0-6 20 0 625 
P-3 0-6 40 0 720 
P-3 0-6 5 5 15400 
P-3 0-6 10 5 1125 
P-3 0-6 20 5 735 
P-3 0-6 40 5 780 
P-3 0-6 5 10 56500 
P-3 0-6 10 10 1050 
P-3 0-6 20 10 835 
P-3 0-6 40 10 832 
P-3 0-6 5 20 41500 
P-3 0-6 10 20 1625 
234 P-3 0-7 0 0 76000 
P-3 0-7 5 0 2150 
P-3 0-7 10 0 3700 
P-3 0-7 20 0 2000 
P-3 0-7 0 5 89000 
P-3 0-7 5 5 88000 
P-3 0-7 10 5 50000 
P-3 0-7 20 5 46500 
P-3 0-7 0 10 102400 
P-3 0-7 5 10 122000 
P-3 0-7 10 10 72000 
P-3 0-7 0 20 113000 
P-3 0-7 5 20 158000 
P-3 0-7 10 20 138000 
235 P-3 0-8 5 0 1925 
P-3 0-8 10 0 1150 
P-3 0-8 20 0 2000 
P-3 0-8 40 0 6200 
236 P-3 0-9 5 0 36000 
P-3 0-9 10 0 1200 
P-3 0-9 20 0 440 
P-3 0-9 40 0 1375 
237 P-3 0-10 5 0 1375 
P-3 0-10 10 0 45500 
P-3 0-10 20 0 625 
P-3 0-10 40 0 510 
238 P-3 0-11 5 0 36000 
P-3 0-11 10 0 20500 
P-3 0-11 20 0 4200 
P-3 0-11 40 0 550 
239 P-3 0-12 0 0 76000 
P-3 0-12 5 0 45000 
P-3 0-12 10 0 24500 
P-3 0-12 20 0 5800 
P-3 0-12 40 0 675 
P-3 0-12 5 5 51500 
P-3 0-12 10 5 28500 
P-3 0-12 20 5 7100 
P-3 0-12 40 5 810 
P-3 0-12 5 10 61200 
P-3 0-12 10 10 33500 
P-3 0-12 20 10 6400 
P-3 0-12 40 10 950 
P-3 0-12 5 20 86800 
P-3 0-12 10 20 40500 
P-3 0-12 20 20 7100 
P-3 0-12 40 20 1350 
240 P-14 0-7 0 0 150000 
P-14 0-7 5 0 1350 
P-14 0-7 10 0 4500 
P-14 0-7 20 0 7000 
P-14 0-7 0 5 140000 
P-14 0-7 5 5 120000 
P-14 0-7 10 5 78000 
P-14 0-7 0 5 140000 
P-14 0-7 5 10 158000 
P-14 0-7 10 10 124000 
P-14 0-7 0 20 136000 
P-14 0-7 5 20 152000 
P-14 0-7 10 20 142000 
241 P-3a 0-2 0 0 132600 
P-3a 0-2 5 0 17300 
P-3a 0-2 10 0 850 
P-3a 0-2 20 0 1425 
P-3a 0-2 40 0 4750 
P-3a 0-2 0 5 140000 
P-3a 0-2 5 5 67000 
P-3a 0-2 10 5 2500 
P-3a 0-2 20 5 3000 
P-3a 0-2 0 10 134000 
P-3a 0-2 5 10 33000 
P-3a 0-2 10 10 4000 
P-3a 0-2 20 10 4900 
P-3a 0-2 0 20 144000 
P-3a 0-2 5 20 49000 
P-3a 0-2 10 20 8000 
242 P-3a 0-3 5 0 28500 
P-3a 0-3 10 0 880 
P-3a 0-3 20 0 1425 
P-3a 0-3 40 0 4600 
P-3a 0-3 5 5 80000 
P-3a 0-3 10 5 2950 
P-3a 0-3 20 5 3200 
P-3a 0-3 40 5 6200 
P-3a 0-3 5 10 78000 
P-3a 0-3 10 10 5200 
P-3a 0-3 20 10 6400 
P-3a 0-3 5 20 136000 
P-3a 0-3 10 20 20500 
243 P-3a 0-4 5 0 94000 
P-3a 0-4 10 0 29000 
P-3a 0-4 20 0 1050 
P-3a 0-4 40 0 850 
P-3a 0-4 5 5 107400 
P-3a 0-4 10 5 39000 
P-3a 0-4 20 5 1225 
P-3a 0-4 40 5 900 
P-3a 0-4 5 10 134000 
P-3a 0-4 10 10 41000 
P-3a 0-4 20 10 1350 
P-3a 0-4 40 10 1050 
P-3a 0-4 5 20 164000 
P-3a 0-4 10 20 33000 
P-3a 0-4 20 20 1825 
P-3a 0-4 40 20 1350 
244 P-3a 0-5 5 0 93500 
P-3a 0-5 10 0 136000 
P-3a 0-5 20 0 178000 
245 P-3a 0-7 5 0 2700 
P-3a 0-7 10 0 6100 
P-3a 0-7 20 0 11900 
__________________________________________________________________________ 
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.