Progress in Polymer Science 36 (2011) 1558–1628

Contents lists available at ScienceDirect

Progress in Polymer Science

journal homepage: www.elsevier.com/locate/ppolysci

Polymers for enhanced oil recovery: A paradigm for

structure–property relationship in aqueous solution
D.A.Z. Wever a,b,1 , F. Picchioni a,2 , A.A. Broekhuis a,∗
a
Department of Chemical Engineering - Product Technology, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands
b
Dutch Polymer Institute DPI, P.O. Box 902, 5600 AX Eindhoven, The Netherlands

a r t i c l e i n f o a b s t r a c t

Article history: Recent developments in the field of water-soluble polymers aimed at enhancing the aque-
Received 2 June 2010 ous solution viscosity are reviewed. Classic and novel associating water-soluble polymers
Received in revised form 3 May 2011
for enhanced oil recovery (EOR) applications are discussed along with their limitations.
Accepted 6 May 2011
Particular emphasis is placed on the structure–property correlations and the synthetic
Available online 27 May 2011
methods. The observed rheological properties are conceptually linked to the polymer chem-
ical structure (1) and topology (2). In addition, the influence of external parameters, e.g.
Keywords:
Water soluble polymers temperature, pH, salt, and surfactant, on the rheological behavior is reviewed. Progress
Enhanced oil recovery (EOR) booked in deeper understanding of the structure–property relationship is thoroughly dis-
Hydrophobically modified polymers cussed. Furthermore, a critical overview of the synthetic methods as well as of the solution
Polyacrylamide properties of these polymers is provided. In this respect the influence of “internal” (i.e.
Associating polymers chemical structure) and “external” (vide supra) factors on these properties provide a con-
Solution rheology ceptual toolbox for the rationalization of the response of water-soluble polymers to external
stimuli. In turn, such rationalization constitutes the basis for the design of new polymeric
structures for EOR applications.
© 2011 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1560
2. Currently used EOR polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1561
2.1. Polyacrylamide (PAM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1561
2.2. Partially hydrolyzed polyacrylamide (HPAM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1561
2.2.1. HPAM chemical structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1561
2.2.2. Rheological properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1563
2.3. Xanthan gum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1565
3. Recent developments in water-soluble thickening polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1566
3.1. Hydrophobically modified polyacrylamide (HMPAM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1567
3.1.1. Chemical structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1581
3.1.2. Rheological properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1583
3.2. Hydrophobically modified ethoxylated urethane (HEUR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1589
3.2.1. Rheological properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1599
3.2.2. Effects of inherent parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1599

∗ Corresponding author. Tel.: +31 050 363 4918; fax: +31 050 363 4479.
E-mail addresses: D.A.Z.Wever@rug.nl (D.A.Z. Wever), F.Picchioni@rug.nl (F. Picchioni), A.A.Broekhuis@rug.nl (A.A. Broekhuis).
1
Tel.: +31 050 363 4461; fax: +31 050 363 4479.
2
Tel.: +31 050 363 4333; fax: +31 050 363 4479.

0079-6700/$ – see front matter © 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.progpolymsci.2011.05.006
 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628 1559

3.2.3. Effects of external parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1600

3.3. Hydrophobically modified alkali swellable emulsion (HASE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1602
3.3.1. Rheological properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1603
3.3.2. Effect of inherent parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1608
3.3.3. Effect of external parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1609
3.4. Hydrophobically modified cellulose derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1610
3.4.1. Rheological properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1611
3.4.2. Effect of inherent parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1617
3.4.3. Effect of external parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1617
4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1619
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1619
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1619

Nomenclature
CMC critical micelle concentration
4-BA 4-butylaniline CS* critical surfactant concentration
AA acrylic acid CTA chain transfer agent
ABS alkylbenzenesulfonates CTAB cetyltrimethyl ammonium bromide
ACVA 4,4 -azobis-4-cyanopentanoic acid CTAT cetyltrimethyl ammonium p-toluenesul-
AGE alkylglycidyl ether fonate
AM acrylamide Da dalton
AMM associative macromonomer DAAM diacetone acrylamide
AMPDAB 4-(2-acrylamido-2- DADMAC N,N-diallyl-N,N-dimethylammonium
methylpropyldimethylammonio) chloride
butanoate DADPMA [(dimethylammonioethoxy)-
AMPDAC 2-(acrylamido-2- dicyanoethenolate]propyl-
methylpropyldimethylammonium) methacrylamide
chloride DAGE (3,3-dialkoxymethyl)propylglycidyl ether
AMPDAE 2-(2-acrylamido-2- DAMA N,N-diallyl-N,N-methylamine chloride
methylpropyldimethylammonio) DAMAPS 3-(N,N-diallyl-N-
ethanoate methylammonoi)propanesulfonate
AMPDAH 6-(2-acrylamido-2- DEmMA substituted methacrylate
methylpropyldimethylammonio) DiC3 AM N,N-dipropylacrylamide
hexanoate DiC6 AM N,N-dihexylacrylamide
AMPDAPS 3-(2-acrylamido-2-methylpropane- DiC8 AM N,N-dioctylacrylamide
dimethylammonio)-1-propanesulfonate DiC10 AM N,N-didecylacrylamide
AMPTAC 2-(acrylamido)-2- DiC12 AM N,N-didodecylacrylamide
methylpropyl]trimethylammonium DiC14 AM N,N-ditetradecylacrylamide
chloride DiC16 AM N,N-dihexadecylacrylamide
APS N-[(1-pyrenylsulfonamido)ethyl]acrylamide DMSO dimethylsulfoxide
BD bromododecane DR drag reduction
BPAM N-(4-butyl)phenylacrylamide DTAB dodecyltrimethylammonium bromide
CAC critical association concentration DTAC dodecyltrimethylammonium chloride
C8 AM octylacrylamide EФAM N-(4-ethyl-phenyl)acrylamide
C10 AM decylacrylamide EA ethyl acrylate
C12 AM dodecylacrylamide EHEC ethyl hydroxyethyl cellulose
C14 AM tetradecylacrylamide EO ethylene oxide
C18 AM octadecylacrylamide EOR enhanced oil recovery
CN AM alkylacrylamide EP16 1,2-epoxyhexadecane
C12 Acl dodecyl ammonium chloride EVE ethyl vinyl ether
C16 TAAc hexadecyltrimethyl ammonium acetate FX-13 2-(N-ethylperfluorosulfoamido)ethyl acry-
C12 TABr dodecyltrimethyl ammonium bromide late
C12 TACl dodecyltrimethyl ammonium chloride FX-14 2-(N-ethylperfluoro-
C16 TACl hexadecyltrimethyl ammonium bromide octane/sulfoamido)ethyl methacrylate
CAC critical association concentration HASE hydrophobically modified alkali swellable
CDMAO cetyldimethylamine oxide emulsion
1560 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

H12 MDI bis(4-isocyanateocyclohexyl)methane PDI polydispersity index

HDI hexamethylene di-isocyanate PEO poly(ethylene oxide)
HEC hydroxyethyl cellulose PGSE pulse gradient spin echo
HEUR hydrophobically modified ethoxylated ure- PMAAM N-phenylmethacrylamide
thane ppm parts per million
HHM-HEC hydrophobically–hydrophilically modi- Py pyrene
fied hydroxyethyl cellulose RRF residual resistance factor
HMPAM hydrophobically modified polyacrylamide S-HEC hydrophilically modified hydroxyethyl cel-
HM-CMC hydrophobically modified carboxymethyl lulose
cellulose S-G HEUR step-growth hydrophobically modified
HM-EHEC hydrophobically modified ethyl hydrox- ethoxylated urethane
yethyl cellulose SANS small-angle neutron scattering
HM-HEC hydrophobically modified hydroxyethyl SEC size exclusion chromatography
cellulose SDS (NaC12 S) sodium dodecyl sulfate
HM-HPC hydrophobically modified hydroxypropyl SMR surfactant to micelle ratio
cellulose SOBS sodium octyl benzene sulfonate
HM-polysaccharides hydrophobically modified THF tetrahydrofuran
polysaccharides TMSPMA 3-[tris(trimethylsilyoxy)sily]propyl
HPAM partially hydrolyzed polyacrylamide methacrylate
HTAC hexadecyltrimethylammonium chloride TTAB tetradecyltrimethyl ammonium bromide
IPBC 4-isopropylbenzyl chloride
IPDI isophorone diisocyanate
KDS potassium dodecyl sulfate
LCST lower critical solution temperature
MA maleic anhydride 1. Introduction
MAA methacrylic acid
MAM methacrylamide Enhanced oil recovery (EOR) is a challenging field for
MeEФAM N-methyl-N-(4-ethyl-phenyl)- different scientific disciplines. The importance of this field
acrylamide is highlighted by the number of patents (mainly filed
MO methyleneoxide by multinational companies) involving polymers for EOR.
MWD molecular weight distribution Nevertheless, the limited number of patents filed in the
NaA sodium acrylate last 10 years (less than 25) demonstrates the difficulty
NaAMB sodium 3-acrylamido-3-methylbutanoate of this research field as well as the relative maturity in
NaAMPS sodium 2-acrylamido-2-methylpropane- the scientific and technological concepts linked to rele-
sulfonate vant applications. Given the fact that the easily recoverable
NaC10 S sodium decyl sulfate oil is running out and that much oil remains in the reser-
NaC14 S sodium tetradecyl sulfate voir after conventional methods have been exhausted, the
NaC12 (EO)2 S sodium dodecyl-di(ethyleneoxide)- implementation of EOR is crucial to guarantee a contin-
sulfate uing supply. In addition, alternative energy sources have
NAEA 2-(1-naphthylacetyl)ethyl acrylate not yet proved to be capable of meeting the world energy
NAEAm 2-(1-naphthylacetamido)ethyl acrylamide demand, so that a mixture of different sources, includ-
NaMAMB sodium 3-methacrylamido-3-methylbu- ing oil, is required to meet the world energy demand
tanoate in the near future. According to Thomas [1], approxi-
NBAM N-benzylacrylamide mately 7.0 × 1012 barrels of oil will remain in oilfields after
NIPAM N-isopropylacrylamide conventional methods have been exhausted; this value
NNDAM N,N-dimethyl acrylamide constitutes also the target recovery for EOR. Water-soluble
nm nanometer polymers for EOR applications have been successfully
NMA [(1-naphthyl)methyl]acrylamide implemented, mainly in Chinese oilfields [2,3]. The pur-
NMR nuclear magnetic resonance pose of the water-soluble polymers in this application is to
NP nonylphenol ethoxylates enhance the rheological properties of the displacing fluid.
NPEAM N-phenethylacrylamide The oil production increases with the microscopic sweep
NRET non-radiative energy transfer of the reservoir and the displacement efficiency of the oil
OG n-octyl ␤-d-glucopyranoside [4]. Indeed, the use of water-soluble polymers improves
OOIP original oil in place the water–oil mobility ratio [4], and leads to enhanced oil
OTG n-octyl ␤-d-thioglucopyranoside recovery. However, given the harsh conditions present in
PAA poly(acrylic acid) most oil reservoirs, new problems and limitations arise
PAGE poly(alkylglycidyl ether) with the use of water-soluble polymers. Besides positively
PAM polyacrylamide affecting solution rheology, water-soluble polymers should
withstand high salt concentration, the presence of calcium,
 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
high temperatures (>70 ◦ C) and long injection times (at
least 12 months) [4,5]. High salt concentrations reduce the
thickening capability of most ionic water-soluble polymers
while the presence of calcium leads to flocculation [6].
New water-soluble polymers were successfully tested at
higher temperatures [7,8]. Associative water-soluble poly-
mers were tested and showed promising results compared
to traditionally used polymers [9,10].
Several studies [11–16] demonstrated that the oil is pro-
duced faster (compared to water flooding), but also more
oil can be recovered. A mechanism based on the visco-
elastic properties of the polymers has been proposed to
explain the higher oil recovery. This mechanism is mainly
supported by indirect evidence and mathematical models
[11–14].
Independently of the exact displacement mechanism
and efficiency, the use of water-soluble polymers for EOR
still constitutes a challenging field, at both industrial and
academic levels. Moreover, the broad variety of polymers
studied for EOR, at least at the academic level, clearly
suggests this research field as paradigmatic for water-
soluble polymers in general. Indeed, fundamental scientific
studies linked to EOR, particularly those involving the
relationship between the polymer structure and the cor-
responding properties in aqueous solution (e.g. viscosity),
have a conceptual character, thus providing a broad and
general understanding, valid also for other “application”
fields. The interaction between polymer chains in aque-
ous solution as well as the influence of the solute structure
on the corresponding viscosity are of paramount impor-
tance in EOR applications, but are studied and modeled
through very general methods and theories. This general
interest in structure–property relationships is testified by
the constantly increasing amount of scientific literature
that is dedicated to this topic [17–20], the last dedicated
review (from 1990 [21]) being already outdated by the
most recent findings. As a consequence, the present review
paper concentrates on different water-soluble polymers
for EOR by discussing their (associative) behavior in water
solution and outlining the most general concepts that
can be learned from the corresponding scientific litera-
ture.
Section 2 presents some background information on
oil recovery methods, thus defining the subject in terms
of polymeric systems reviewed in this work. In Section
3 the synthetic methods used for the different polymers
are discussed, including the effect of the relationship
between the process conditions employed and the cor-
responding polymer chemical structure. Subsequently,
the chemical structures are linked to the corresponding
rheological properties in water solution. The sensitiv-
ity of the rheological behavior is also elucidated as a
function of external parameters, such as (the presence
of) mechanical shear, solution temperature, electrolyte
type and concentration, pH, ionic strength and sur-
factant type and concentration. Relations between the
polymer structure, i.e. chemical structure and topol-
ogy, are proposed for the different polymers. Finally,
in Section 4 we provide some general conclusions on
the most recent, relevant and generally accepted con-
cepts.
1561
2. Currently used EOR polymers
2.1. Polyacrylamide (PAM)
Polyacrylamide was the first polymer used as thickening
agent for aqueous solutions. The thickening capabil-
ity (increase of the corresponding solution viscosity) of
PAM resides mainly in its high molecular weight, which
reaches relatively high values (>1 × 106 g/mol). In the gen-
eral framework of EOR processes, PAM is mainly used
as the reference “model system” for chemical modifi-
cation. Many authors have reported different attempts
to alter the chemical structure of PAM or to synthe-
size new acrylamide-based copolymers with improved
properties, i.e. shear resistance, brine compatibility and
temperature stability [22–25]. The synthesis of the copoly-
mer N,N-dimethyl acrylamide with Na-2-acrylamido-2-
methylpropanesulfonate (NNDAM–NaAMPS) was reported
by Sabhapondit et al. [22,23] and tested for its perfor-
mance in EOR applications. The stability of the polymer at
high temperature was demonstrated by ageing at 120 ◦ C
for 1 month [22]. By using a sand pack, an improved
performance in terms of EOR for the NNDAM–NaAMPS
copolymer [23] as compared to unmodified partially
hydrolyzed polyacrylamide, HPAM, was demonstrated.
In another example, Song et al. [24] reported the syn-
thesis of starch-graft-poly(acrylamide-co-(2-acrylamido-
2-methylpropanesulfoacid)). The oil recovery rate of the
subsequent polymer solution was higher compared to
HPAM, and the novel polymer displayed better temper-
ature and shear stability. These two examples already
define a common research theme in the general field
of water-soluble polymers for EOR. That is, a strategic
approach involving the chemical modification of commer-
cial polymers (in this case PAM) to tailor and improve the
corresponding solution properties and eventually EOR per-
formance.
2.2. Partially hydrolyzed polyacrylamide (HPAM)
HPAM, by far the most used polymer in EOR applica-
tions, is a copolymer of PAM and PAA obtained by partial
hydrolysis of PAM or by copolymerization of sodium acry-
late with acrylamide [21].
2.2.1. HPAM chemical structure
The chemical structure of HPAM is provided in Fig. 1.
In most cases the degree of hydrolysis of the acrylamide
monomers is between 25 and 35% [4,26]. The fact that
a relevant fraction of the monomeric units needs to be
hydrolyzed (lower limit of 25%) is probably related to the
Fig. 1. Chemical structure of HPAM.
1562 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
formation of the corresponding salt. According to the gen-
eral theory of polyelectrolyte solutions [27], the presence of
electrostatic charges along a polymer backbone is respon-
sible for prominent stretching (due to electric repulsion)
of the polymeric chains in water and, eventually, results
in a viscosity increase compared to the uncharged ana-
logue. On the other hand, according to a study by Shupe
[28] the degree of hydrolysis cannot be too high because
the polymer solution will become too sensitive to salinity
and hardness of the brine (electrolytes present in solution
have a “shielding effect” on the electrostatic repulsion).
Indeed, polyelectrolytes, i.e. polymers bearing charges,
show significantly different rheological behavior compared
to their neutral analogues [29–31]. The thickening capabil-
ity of HPAM lies in its high molecular weight and also in the
electrostatic repulsion between polymer coils and between
polymeric segments in the same coil [4]. When poly-
electrolytes are dissolved in water containing electrolytes
(salts) a reduction in viscosity is observed [26,32–34]. It
has been demonstrated that the specific viscosity of HPAM
solutions depends on the amount of salt present [35]. This
effect is attributed to the shielding effect of the charges
[4,33] leading in turn to a reduction in electrostatic repul-
sion and consequently to a less significant expansion of the
polymer coils in the solution. This results in a relatively
lower hydrodynamic volume, which is synonymous with a
lower viscosity [34]. A few decades ago, substitution of one
or both hydrogens on the amide nitrogen with alkyl groups
Fig. 2. Complexation behavior of HPAM under different conditions.
Reproduced with permission from [39] 1999, ACS Publishing.
has been presented as a solution to the salt sensitivity of the
HPAM [36,37], although the exact reasons for this behavior
have not been fully elucidated.
The addition of monovalent NaCl leads to a reduction in
the level of aggregation. However, at higher ionic strengths
(higher salt concentration) the addition of NaCl leads to
macroscopic flocculation [38]. It has also been demon-
strated that multivalent cations can form polyion–metal
complexes which affect the viscosity of the resulting solu-
tion [39–41]. A study by Peng and Wu [39] investigated the
dependence of the self-complexation of HPAM on the Ca2+
concentration and the degree of hydrolysis of HPAM. They
demonstrated that depending on the Ca2+ concentration
intrachain and interchain complexations take place (Fig. 2)
[39].
Besides the salt dependency, other factors influencing
the viscosity of HPAM solutions are the degree of hydrol-
ysis, solution temperature, molecular weight and solvent
quality [35]. Pressure also affects the viscosity of HPAM
solutions. According to a study by Cook et al. [42] the
increase in the viscosity of the HPAM solutions cannot
solely be accounted for by the increase in viscosity of the
solvent. The intrinsic viscosity and the radius of gyration
are both invariant with pressure, albeit with a 10% exper-
imental uncertainty [42]. In principle, the dimensions of
the polymer coils do not change while the solvent volume
decreases. Therefore the volume fraction of the polymer
coil per unit volume of the solvent increases, hence a higher
 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
Fig. 3. Schematic presentation of behavior of HPAM coils in shear flow.
Reproduced with permission from [46] 1995, ACS Publishing.
viscosity [42]. Another parameter that affects the solution
viscosity of the polymer solution is shear [43]. Under high
shear the HPAM polymer chains are reduced in size due
to chain scission, i.e. fragmentation [44]. This leads to a
reduction in the solution viscosity.
2.2.2. Rheological properties
HPAM is preferred in EOR applications since it can toler-
ate the high mechanical forces present during the flooding
of a reservoir. In addition, HPAM is a low cost polymer
and is resistant to bacterial attack [4]. Although the HPAM
solutions display pseudoplastic behavior [4,26,32,45,46]
(shear thinning) in simple viscometers, it has been demon-
strated that these solutions show pseudodilatant [47,48]
characteristics (shear thickening) in porous media as well
as in viscometers at relatively high shear rates. Research
has demonstrated the presence of a critical shear rate at
which the shear thickening behavior arises in viscometers
[32,33,45,46,49,50]. This critical shear rate depends on the
degree of hydrolysis of the HPAM, the solution concentra-
tion, the temperature, the quality of the solvent and also on
the molecular weight of the polymer [33,45]. An increase
in the degree of hydrolysis leads to an onset of shear thick-
ening at lower shear rates [45]. By decreasing the average
molecular weight, an increase in the polymer concentra-
tion results in a higher critical shear rate [45,46].
The aforementioned shear thinning of HPAM solutions
below a critical shear rate arises due to uncoiling of poly-
mer chains and the dissociation of entanglements between
separate polymer coils [4]. Stiffening of the polymer back-
bone has been suggested as a possible approach to control
the dependency of HPAM polymer solutions on the shear
[51]. A stiff polymer will have a lower mobility and there-
Fig. 4. Type I and II of rheopectic behavior of HPAM solutions.
Reproduced with permission from [58] 1995, Springer.
1563
fore the entanglements, related to the solution viscosity,
will be conserved as the shear increases.
The shear thickening behavior has been attributed to
changes in the molecular conformation involving the for-
mation of additional links between two chains [49]. The
shear thickening behavior is observed both in laboratory
rheometers [45] (in pure water and aqueous salt solu-
tions) and in porous media. According to several studies
the shear thickening behavior in porous media arises due
to coil-stretched transitions of the polymer chains. The
structure of a porous medium can be seen as alternating
wide openings and confined throats through which the
polymer coils have to navigate. In the wide openings the
polymer chains attain a coil structure. When these coils
then have to pass through a narrow throat the polymer
coils are forced to deform and stretch (elongational strain
[32,48,52]) in order to pass. This successive contraction
and expansion of the polymer coils leads to pseudodilatant
behavior of the polymer solutions [48,53,54]. This con-
formational change of the macromolecules is reversible
since it is commonly explained by formation at macro-
molecular level of reversible interactions like hydrogen
bonding. Indeed, it is believed that hydrogen bonding arises
for HPAM solutions between the carboxylic functional-
ities [55]. However, this is contested due to conflicting
data [49,56] on similar polymeric solutions (e.g. dextran
solution). Instead, aggregation of hydrophobic bonds has
been proposed [55], albeit in polymethacrylic acid, but this
has not been confirmed [57]. Hu et al. [46] proposed a
schematic presentation depicting the essential behavior of
HPAM solutions in shear flow (see Fig. 3).
Another behavior that has been identified for HPAM
solutions which is important for EOR is their negative
1564 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
Fig. 5. Interactions between sodium oleate and HPAM at low (A) and high (B) surfactant concentration.
thixotropic (rheopectic) property, i.e. an increase in vis-
cosity with shear-time at a constant shear rate [32,58–61].
Researchers have identified two different types of rheopec-
tic behavior for HPAM solutions (Fig. 4), type I and type
II [58]. The type I effect is observed at low shearing and
consists in a slow viscosity increase with shear-time up
to an asymptotic value. The type II effect is seen at high
shear rates and is displayed as a steep viscosity increase
after a given shear-time, followed by pronounced viscosity
oscillation [58].
2.2.2.1. Effect of inherent parameters on rheology. For HPAM
the degree of hydrolysis has a significant impact on the
rheological properties of the subsequent solution. If the
hydrolysis degree of HPAM is too large, insolubility prob-
lems can arise. When too small, a large dependence of
the solution viscosity on electrolyte presence is observed.
Lewandowska [45] investigated the effect of the degree of
hydrolysis on the solution viscosity in a NaCl solution. If
the degree of hydrolysis is increased the zero shear rate
viscosity and the critical shear rate for the onset of shear
thickening are both reduced. The shear rate region where
the shear thinning behavior is observed is reduced with the
increase in the degree of hydrolysis [45,46,62].
Another inherent parameter of HPAM is its molecular
weight. Increase of the molecular weight will lead to a more
pronounced shear thinning behavior. The critical shear rate
for the onset of shear thickening is also affected by the
molecular weight in that it is increased with an increase
in the molecular weight [45].
2.2.2.2. Effect of external parameters on rheology. The influ-
ence of salt (NaCl) addition on the rheological behavior
of HPAM solutions has also been extensively studied. It
was found that, below the critical shear rate, adding salt
reduced the extent of shear thinning while above the crit-
ical shear rate the amplitude of the shear thickening is
increased [32]. The zero shear rate solution viscosity is also
reduced as the concentration of salt increases [4].
Adding salt to the solvent will reduce the extent of the
rheopectic behavior of the polymer solution [59]. Looking
more closely to the effect of salt, addition of mono-valent
cations (e.g. NaCl) was found to increase the onset (i.e. the
critical shear rate value) of rheopectic behavior type I while
for type II no changes were observed [58]. When using
multivalent cations (CaCl2 and AlCl3 ) the effect seen with
mono-valent cations is amplified, i.e. the effect is seen at
lower cation concentrations [61]. This is due to the higher
screening capability of multivalent cations [61]. In addi-
tion a reduction of the degree of hydrolysis leads to a less
prominent rheopectic behavior of type I [60].
Besides salts, also surfactants are able to interact with
polymer chains in solutions and thus display a relevant
influence on the corresponding rheological behavior. Xin
et al. [63] investigated the interaction between the surfac-
tant sodium oleate and HPAM and found that the viscosity
of the polymer–surfactant aqueous solution depends on
the surfactant concentration. At low surfactant concentra-
tion an enhancement of the viscosity is observed due to
interpolymer cross-linking of the surfactant and HPAM. At
high surfactant concentration the repulsion between the
micellar aggregates attached to the polymer increases and
this leads to a decrease in the hydrodynamic volume and
thus a decrease in the solution viscosity. The authors [63]
have proposed a model depicting the interactions between
HPAM and sodium oleate (a surfactant) at low and high
concentration of the latter (Fig. 5).
Interchain cross-linking arises due to hydrogen bond-
ing. At high surfactant concentration repulsion between
the surfactant molecules dominates and this leads to
the collapse of the network between the surfactant and
HPAM, which in turn results in a reduction of the vis-
cosity. Methemitis et al. [64] investigated the interactions
between SDS and HPAM and concluded that the effect of the
surfactant on the rheological properties of HPAM depends
on the pH of the solution and the presence of electrolyte.
When no effort is devoted at altering the pH of the solu-
tion, a reduction in the solution viscosity is observed up
to the CMC of the surfactant either in water or in salty
water. Above the CMC the solution viscosity of the ternary,
system, i.e. water–polymer–surfactant, remains relatively
constant with further addition of SDS in the salty water. In
pure water the solution viscosity still decreases with fur-
ther addition of SDS. If the pH of the solution is reduced (to a
pH of 2.5) the solution viscosity decreases until the CMC of
the surfactant is reached, after which a significant increase
is observed with further addition of SDS. The authors have
hypothesized that at low pH fixation of some protons onto
the surfactant micelles occurs [64]. This changes the ion-
ization equilibrium of the carboxylic groups leading to an
increase in the surface charge density, which corresponds
to an increase in solution viscosity.
 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
Fig. 6. Chemical structure of xanthan gum.
2.3. Xanthan gum
Xanthan gum is a polysaccharide, which is produced
through fermentation of glucose or fructose by different
bacteria [65]. The most efficient xanthan gum producer is
the Xanthomonas campestris bacterium [65,66]. The chem-
ical structure of xanthan gum (Fig. 6) displays the presence
of two glucose units, two mannose units and one glucuronic
acid unit with a molar ratio of 2.8–2.0–2.0 [67]. The back-
bone of xanthan gum is similar to cellulose. The side chains
of the polymer contain charged moieties, i.e. acetate and
pyruvate groups, and the polymer is thus a polyelectrolyte.
However the classic polyelectrolyte behavior according to
which the solution viscosity decreases with the addition of
salt is not displayed in this case. The thickening capability
of xanthan gum lies in its high molecular weight, which
ranges from 2 to 50 × 106 g/mol [67,68] and in the rigidity
of the polymer chains.
It has been demonstrated that upon addition of salt
(mono or divalent) the xanthan gum chains undergo a
cooperative conformational transition from a disordered
conformation to an ordered and more rigid structure
[69–72] (Fig. 7).
The temperature and the ionic strength (the amount
of electrolyte) of electrolyte, of the solution are triggers
for the conformational transition. When testing at low
shear, the rheology of the polymer solution is dependent
on the conformation with the disordered conformation
displaying higher solution viscosities [73]. Polymeric solu-
Fig. 7. Conformational transition of xanthan gum.
1565
tions employing xanthan gum display high viscosity at
low shear rates [74] and thus the disordered conforma-
tion predominates at low shear rates. At high shear rates
both conformations display similar rheological behaviors
[73]. In addition, pseudoplastic behavior is observed for
the polymer solutions [75]. Unlike HPAM, xanthan gum
displays good resistance to high temperatures. It was
demonstrated that the solution viscosity of a polymeric
solution employing a commercial xanthan gum remained
relatively constant for more than 2 years at 80 ◦ C [76]. Loss
of solution viscosity occurs at temperature above 100 ◦ C.
Several studies [77–80] have investigated the temperature
dependence of the apparent viscosity of xanthan gum solu-
tions. In order to display resistance to temperatures up
to 90 ◦ C, the conventional understanding for xanthan gum
solutions is that the ionic strength of the solution has to be
relatively high. Another positive property of xanthan gum
is its ability to withstand high shear forces. Unlike HPAM
the solution viscosity does not decrease at relatively high
shear stresses [47]. Especially the ordered structure, i.e. in
the presence of salt, can withstand high shear forces [73]
(up to a shear rate of 5000s−1 ).
A disadvantage of xanthan gum is its susceptibility
to bacterial degradation. It has been demonstrated that
salt tolerant aerobic and anaerobic microorganisms can
degrade the xanthan gum chains which leads to the loss
in solution viscosity [81–84]. Biocides are used to suppress
the growth of the xanthan gum degrading microorganisms.
In most cases formaldehyde is the most efficient biocide
1566 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
[83,84]. However the use of biocides to protect the xanthan
gum renders the low environmental impact of the polymer
obsolete.
Combinations of xanthan gum with surfactants have
also been studied. It has been demonstrated that the com-
bination can be beneficial. According to Taugbol et al. [85]
more than 50% of the residual oil (after a waterflood) can be
recovered using xanthan gum and an alkyl propoxy-ethoxy
sulfate (C12–15 (PO)4 -(EO)2 -OSO3 − Na+ ) as the surfactant.
The recovery of the residual oil using only a surfactant solu-
tion was lower. However it has been demonstrated that
the combination of xanthan gum and dodecyl-o-xylene
sulfonate recovered less of the residual oil compared to
the case where only a surfactant solution was used [86].
According to the authors a possible explanation is the for-
mation of large micellar aggregates, which have a negative
effect on the flow performance of the surfactant through
the porous media.
3. Recent developments in water-soluble
thickening polymers
The limited number of available commercial poly-
mers currently employed in EOR has been the subject
of recent developments aimed at improving their perfor-
mance. Indeed, an alternative concept has been studied in
the last four decades, and involves the association between
hydrophobic groups that are incorporated in the back-
bone of the polymers [87]. Through these associations a
higher thickening capability can be achieved compared to
the traditional polymers [87]. Several different types of
associating polymers have been studied. These include the
hydrophobically modified polyacrylamide (HMPAM) [88],
ethoxylated urethane (HEUR) [89], hydroxyethylcellulose
(HMHEC) [90] and alkali-swellable emulsion (HASE) [91].
Also combinations of associative polymers with surfactants
have been developed for EOR [92]. It has been demon-
strated that the addition of small amounts of surfactants
Fig. 8. Intra- and intermolecular associations.
Reproduced with permission from [132] 1996, ACS Publishing.
can increase the viscosity of the aqueous solution contain-
ing hydrophobically modified polymers significantly [90].
Other polymers that posses interesting properties,
such as high molecular weight and intrinsic viscosity,
have been developed for EOR and are known as “rigid
rod” water-soluble polymers [93]. One study compared
hydrophobically modified polyacrylamide (HMPAM) with
polyacrylamide (PAM) in a simple core flood test and
demonstrated that the residual resistance factor (RRF) after
the polymer flood is much higher for the HMPAM compared
to PAM [94]. All these modification strategies, together
with new kinds of water-soluble systems, have been exten-
sively reported in the literature and will be discussed in the
next paragraph.
As mentioned earlier, a relatively new class of water-
soluble polymers is the one constituted by hydrophobically
associative polymers [87]. The first hydrophobically asso-
ciative polymers were synthesized almost fifty years ago
[95,96], albeit for a different purpose than EOR. Indeed, the
research on these types of polymers has been primarily
fueled by the coating industry [87], where improvement
in the rheology of the coating systems was required. Dur-
ing the 1980s when the oil crisis hit, a lot of research was
performed on EOR. From the many patents [97–102] that
have been filed during those years it is evident that this
accelerated the development of hydrophobically associa-
tive polymers for use in EOR applications.
Hydrophobically associative polymers contain, in
most cases, a small number of hydrophobic groups,
i.e. 8–18 carbon atoms moieties [103–106], distributed
along the main backbone [20,107,108]. These hydropho-
bic groups can be distributed randomly or block-like
[88,91,103,107,109–120], and coupled at one or both
ends [104,121–131]. Above a given polymer concentration
(dependent on the molecular structure) the hydropho-
bic groups associate, when the polymer is dissolved
in water, to form hydrophobic micro-domains (intra or
intermolecular liaisons) [88,89,104,105,107,108,132–135].
These lead to an increase in hydrodynamic volume, which
 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
in turn yields a polymer with a much better thickening
(higher viscosity [107]) capability compared to its non-
associative analogue [88]. Depending on the concentration,
intra- or intermolecular associations are formed, which are
schematically illustrated in Fig. 8.
When the hydrophobic elements are distributed in a
block-like fashion along the backbone of a water-soluble
copolymer, the intramolecular associations are stronger
compared to randomly or discretely distributed hydropho-
bic groups [104,121].
The temperature dependence of the solution viscos-
ity is an interesting property of hydrophobically modified
polymers for EOR applications. It has long been accepted
that increasing the temperature of the polymer solution
will lead to a reduction in viscosity [103,133,136–140].
This since an increase in temperature implies a decrease
of the association strength of the hydrophobes. Increas-
ing the temperature of the solution leads to a reduction
of the solvent viscosity and hence an increase in the
mobility of the polymer chains while the solubility of the
polymer will increase with temperature. However, many
different aqueous systems have been demonstrated to
display an increase in viscosity upon increasing the tem-
perature [141–154]. Indeed, a temperature increase will
decrease the solubility of one of the components (lower
critical solution temperature [LCST]-groups) of the poly-
mers. These less soluble components will self-aggregate
with the hydrophobic groups of the polymers, which leads
to an increase in viscosity [119]. Several researchers have
proposed a concept for thermo-associative polymers based
on the switch, i.e. the transition between low and high
temperature, of the polymers characterized by a lower
critical solution temperature [140,151,152]. The concept
involves a highly water-soluble polymer containing blocks
or side chains of LCST groups. Upon heating of the polymer
solution, these LCST groups will segregate. A schematic pre-
sentation of this behavior has been presented by Hourdet
and coworkers [151] and is depicted in Fig. 9.
Above the critical overlap chain concentration this tran-
sition will lead to an increase in the viscosity of the solution
through intermolecular associations.
Fundamental research on different polymers, in binary
(polymer–water) and ternary (polymer–water–surfactant)
systems, has been performed using different techniques
which include 13 C NMR [155–158] (solution or solid-
state), 1 H NMR [109], 23 Na NMR [159,160], 19 F NMR
[161], NMR self-diffusion [126,162–165] potentiome-
try [166–168], static and dynamic laser light scatter-
ing [128,130,131,146,163,167–172], UV-spectroscopy for
polymers bearing chromophores [88,110,111,173–181],
small-angle neutron scattering (SANS) [182], non-radiative
energy transfer (NRET) studies [178,183–185], size exclu-
sion chromatography (SEC) [170,186–189] and surface
tension [131,133,162,163,165].
Several different associative hydrophobically modified
polymers have been developed which include polyacry-
lamides (HMPAM), ethoxylated urethanes (HEUR), alkali
swellable emulsions (HASE), and polysaccharides (HM-
polysaccharides). Their synthesis, rheological behavior and
adsorption on surfaces will be discussed in the following
sections.
1567
3.1. Hydrophobically modified polyacrylamide (HMPAM)
HMPAM constitutes the most popular basic structure
for the synthesis of new water-soluble polymers for EOR.
Indeed, as given in Table 1, many types have been pub-
lished.
There are different methods of synthesizing HMPAM
such as micellar [88,113,135], homogeneous [88,248,249]
and heterogeneous [88] copolymerization. Polyacrylamide
is usually prepared via a free radical polymerization in
aqueous solution [88,250]. However, as is evident from
the name, HMPAM cannot be synthesized using this tech-
nique as the hydrophobic monomer is not soluble in
water. In order to disperse the hydrophobic monomer,
it is dissolved using a co-solvent (homogeneous copoly-
merization) or a surfactant (micellar copolymerization) or
dispersed without any additives (heterogeneous copoly-
merization) [88,135].
Among these different methods, micellar copolymeriza-
tion has been mostly studied. It generally involves the use
of a hydrophobic monomer (soluble in micelles stabilized
by a surfactant) and a hydrophilic one which is soluble
in the water phase. The first reports on micellar copoly-
merization appeared simultaneously some 25 years ago
[251–256]. A schematic presentation of this polymeriza-
tion technique is presented in Fig. 10.
When synthesizing polymer 17 (Table 1) Chang
and McCormick [220] noted that the use of micellar
copolymerization leads to a block-like distribution of the
hydrophobes whereas solution copolymerization leads
to a random distribution. Both polymers exhibit com-
pletely different rheological properties. The same behavior
was observed when synthesizing polymer 29 (Table 1)
using both (micellar and solution) techniques [110,111].
The most popular surfactants in micellar copolymeriza-
tion are sodium dodecyl sulfate (SDS) [92,103,104,109,
112,121,134,135,138,173–179,203,229,230,241,257–260]
and cationic hexadecyltrimethylammonium bromide
(CTAB) [113,133,220,238]. Many different hydropho-
bic monomers have been used, such as acrylate or
methacrylate-derivatives, alkyl groups with vary-
ing number of carbons and different topologies
[99,100,103,229,261–264], aryl or alkylaryl functionalities
[88,110,111,113,173–177,230,260,265–268], fluorocarbon
containing agents [132,241,242,269–271] and zwitterionic
groups [196–199,201–203,234,272–274]. By incorporating
water-soluble spacers between the hydrophilic backbone
and the hydrophobic group an enhancement of the viscos-
ity can be achieved compared to systems without spacers
[199,241]. According to Hwang and Hogen-Esch [241] the
formation of hydrophobic micro-domains is effectively
promoted by increasing the lengths of the spacers.
Parameters affecting the properties of the polymers
prepared by micellar copolymerization are the type
and concentration of the hydrophobic and hydrophilic
monomer [109,174,175,258], the molar ratio between
the two monomers, the content and type of surfactant
[174,275], the content and type of initiator and the tem-
perature of the reaction [135]. Another parameter that has
been identified is the molar ratio between the hydrophobic
monomer and surfactant, i.e. the number of hydrophobic
 1568
Table 1
Structure of different water-soluble polymers, HMPAM.

Polymer Structure References

Polyelectrolyte

Copolymer of acrylamide (AM) and sodium 2-acrylamido-2-methylpropanesulfonate (NaAMPS, R = 2) [190–193]

or sodium 3-acrylamido-3-methylbutanoate (NaAMB, R = 1) or
(2-acrylamido-2-methylpropyl)dimethylammonium chloride (AMPDAC, R = 3)

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

Polyelectrolyte

Copolymer of acrylamide (AM) and sodium 3-methacrylamido-3-methylbutanoate (NaMAMB) [194,195]

Polyelectrolyte, zwitterionic monomer

Copolymer of 3-(2-acrylamido-2-methylpropane-dimethylammonio)-1-propanesulfonate [196]

(AMPDAPS) with 4-(2-acrylamido-2-methylpropyldimethylammonio) butanoate (AMPDAB)

Polyelectrolyte, zwitterionic monomer

Copolymer of acrylamide (AM) with [197]

3-(2-acrylamido-2-methylpropane-dimethylammonio)-1-propanesulfonate (AMPDAPS)
Table 1 (Continued)

Polymer Structure References

Polyelectrolyte, zwitterionic monomer

Copolymer of AM with 2-(2-acrylamido-2-methylpropyldimethylammonio) ethanoate (AMPDAE, [198–200]

N = 1) or AMPDAB, N = 3 or 6-(2-acrylamido-2-methylpropyldimethylammonio) hexanoate
(AMPDAH, N = 5)

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

Polyelectrolyte, zwitterionic monomer

Terpolymer of AM with acrylic acid (AA) and AMPDAPS [201]

Polyelectrolyte, zwitterionic monomer

Terpolymer of AM with sodium acrylate (NaA) and AMPDAB [202]

Polyelectrolyte, zwitterionic monomer

Copolymer of AM with [(dimethylammonioethoxy)dicyanoethenolate]propyl-methacrylamide [203]

(DADPMA)

1569
 1570
Polyelectrolyte, zwitterionic backbone

Terpolymer of AM and AMPDAC (R1 = H) with NaAMPS (R2 = 1) or AMPTAC (R1 = CH3 ) with NaAMPS [204–207]
(R2 = 1) or AMPTAC (R1 = CH3 ) with NaAMB (R2 = 2)

Polyelectrolyte, zwitterionic backbone

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

Terpolymer of AM with AMPDAC and sodium 3-acrylamido-3-methylbutanoate (NaAMB) [208]

Polyelectrolyte, zwitterionic backbone

Copolymer of 2-acrylamido-2-methylpropanesulfonate (NaAMPS) with [209–211]

(2-acrylamido-2-methylpropyl)-dimethylammonium chloride (AMPDAC, R = H) or
[2-(acrylamido)-2-methylpropyl]trimethylammonium chloride (AMPTAC, R = CH3 )

Polyelectrolyte, amphiphilic

Copolymer of AM (R1 = NH2 ) and sulfonate containing monomer (R2 = 1) [115,212,213]

Table 1 (Continued)

Polymer Structure References

Copolymer of NaA (R1 = O− Na+ ) and alkylchains (R2 = 2) or C8F (R2 = 3) or C10F (R2 = 4) or 3-PDCA
(R2 = 5)
Polyelectrolyte, amphiphilic

Copolymer of NaA and [156,214–216]

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

A, Dodecylacrylamide (C12 AM), R = NH, M = 11, N = 0 or
A, Octadecylacrylamide (C18 AM), R = NH, M = 17, N = 0 or
B, Substituted methacrylate (DEmMA), N = 2, 6 or 25) or
Copolymer of NaAMPS and
B, Substituted methacrylate (DEmMA), N = 2, 6 or 25)

Polyelectrolyte, amphiphilic

Terpolymer of AM (R1 = NH2 ) and AA (R2 = OH) with [175,176,217]

N-[(hexyl)phenyl]acrylamide (R3 = 2, N = 5) or
N-[(decyl)phenyl]acrylamide (R3 = 2, N = 10) or
Terpolymer of AA (R2 = OH) and NaAMPS (R2 = 1) with
PEO chain (R3 = 4) or
Terpolymer of AM (R1 = NH2 ) and NaAMPS (R2 = 1) with
N,N-Dihexylacrylamide (DiHexAM, R = 5 and M = 5)

1571
 1572
Polyelectrolyte, amphiphilic

Terpolymer of AA and methacrylamide (MAM) with [185,218]

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

(DiC6 AM, N = 4) N,N-dihexylacrylamide or
(DiC8 AM, N = 6) N,N-dioctylacrylamide or
(DiC10 AM, N = 8) N,N-didecylacrylamide or
(DiC12 AM, N = 10) N,N-didodecylacrylamide or
(DiC14 AM, N = 12) N,N-ditetradecylacrylamide or
(DiC16 AM, N = 14) N,N-dihexadecylacrylamide

Polyelectrolyte amphiphilic

Terpolymer of maleic anhydride (MA), ethyl vinyl ether (EVE) and 4-butylaniline (4-BA) [219]

Polyelectrolyte, amphiphilic

Copolymer of AM (R1 = NH2 ) and dimethyldodecyl(2-acrylamidoethyl)ammonium bromide (DAMAB, [115,220,221]

R2 = 3, R3 = H and M = 2) or dimethyldodecyl(2-methacrylamidopropyl)ammonium bromide
(DMAMAB, R2 = 3, R3 = CH3 and M = 3) or

Copolymer of AA (R1 = OH) and 2-ethylhexyl (R2 = 1) or n-alkyl (R2 = 2)

Table 1 (Continued)

Polymer Structure References

Polyelectrolyte, amphiphilic

Copolymers of N-isopropylacrylamide (NIPAM, R2 = 1) or AA (R2 = OH) with [221–225]

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

2-(N-ethylperfluorosulfoamido)ethyl acrylate (FX-13), R1 = H or
2-(N-ethylperfluoro-octane/sulfoamido)ethyl methacrylate (FX-14), R1 = CH3

Polyelectrolyte, zwitterionic monomer and amphiphilic

Copolymer of 3-(N,N-diallyl-N-methylammonio)propane-sulfonate (DAMAPS, R2 = 1) with [226–228]

N,N-diallyl-N,N-dimethylammonium chloride (DADMAC, R1 = CH3 ) or N,N-diallyl-N-methylamine
chloride (DAMA, R1 = H)

Copolymer of DADMAC, (R1 = CH3 ) with

N,N-Diallyl-N-hexylbeznyl-N-methylammonium chloride (R2 = 2) or
N,N-Diallyl-N-octylbeznyl-N-methylammonium chloride (R2 = 3)

Polyelectrolyte, zwitterionic monomer and amphiphilic

Terpolymer of AM and n-decylacrylamide (C10 AM) with [229]

1573
 1574
NaA, R = O− Na+ or
NaAMB, R = C7 H17 N2 O2 − Na+ or
NaAMPS, R = C4 H9 NSO3 − Na+

Polyelectrolyte, zwitterionic monomer and amphiphilic

Terpolymer of AM and N-(4-butyl)phenylacrylamide (BPAM) with [230]

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

NaA, R = O− Na+ or
NaAMB, R = C7 H17 N2 O2 − Na+ or
NaAMPS, R = C4 H9 NSO3 − Na+

Polyelectrolyte, zwitterionic monomer and amphiphilic

1. Terpolymer of sulfur dioxide, N,N-diallyl-N-carboethoxymethylammonium chloride with [231–234]

N,N-diallyl-N-alkylammonium chloride (R2 = 1) or dendritic quadruple-tailed hydrophobic group
(R2 = 2)
Table 1 (Continued)

Polymer Structure References

2. Terpolymer of sulfur dioxide, 3-(N,N-diallylammonio) propanesulfonate with

N,N-diallyl-N-octadecylammonium chloride
3. Terpolymer of sulfur dioxide N,N-diallyl-N-carboethoxymethylammonium chloride with single-,
twin- and triple-tailed hydrophobic groups (A, B or C)
Amphiphilic

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

Copolymer of AM (R1 = H) and [103,235]

Octylacrylamide (C8 AM, R2 = 1), N = 7 or

Decylacrylamide (C10 AM, R2 = 1), N = 9 or
Dodecylacrylamide (C12 AM, R2 = 1), N = 11 or
t-octylacrylamide (R2 = 2)
n-decylacrylamide (R2 = 3 or 4)
Copolymer of N-isopropylacrylamide (NIPAM, R1 = CH3 ) and
Decylacrylamide (C10 AM, R2 = 1), N = 9 or
Tetradecylacrylamide (C14 AM, R2 = 1), N = 13 or
Octadecylacrylamide (C18 AM, R2 = 1), N = 17

Amphiphilic

Copolymer of AM and [109,138,190,191,236,237]

N-octylacrylamide (OctAM, R = (CH2 )7 –CH3 ) or

Diacetone acrylamide (DAAM, R = 1) or

1575
 1576
N-hexylacrylamide (HexAM, R = 2) or
N-methyl-N-hexylacrylamide (MeHexAM, R = 3) or
N,N-dihexylacrylamide (DiHexAM, R = 4 and N = 5) or
di-n-propylacrylamide (DPAM, R = 4 and N = 2) or
di-n-octylacrylamide (DOAM, R = 4 and N = 7) or
N-(4-ethyl-phenyl)acrylamide (EAM, R = 5) or

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

N-methyl-N-(4-ethyl-phenyl)-acrylamide (MeEAM, R = 6) or
BPAM, R = 7

Amphiphilic

Copolymer of AM and [133,238,239]

N-benzylacrylamide(NBAM, R1 = H and R2 = (CH2 )1 )

N-phenethylacrylamide(NPEAM, R1 = H and R2 = (CH2 )2 )
N-phenylmethacrylamide(PMAAM, R1 = CH3 and R2 = NH)

Amphiphilic

Copolymers of acrylic acid (AA) and [240]

3-[tris(trimethylsilyoxy)sily]propyl methacrylate (TMSPMA)

Table 1 (Continued)

Polymer Structure References

Amphiphilic

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

Copolymer of AM and [132,241–243]

1,1-Dihydroperfluorobutyl acrylate (2a) or

1,1-Dihydroperfluorooctyl acrylate (2b) or
2-(N-ethylperfluorooctanesulfonamido)ethyl acrylate, FOSA (3a) or
2-(N-ethylperfluorooctanesulfonamido)ethyl methacrylate, FOSM (3b) or
1,1-Dihydroperfluorooctylmono-(ethyleneoxy) acrylate (4a) or
1,1-Dihydroperfluorooctylbis-(ethyleneoxy) acrylate (4b) or
1,1-Dihydroperfluorooctyltris-(ethyleneoxy) acrylate (4c) or
Dodecyl acrylate (5a) or
Dodecylmono-(ethyleneoxy) acrylate (5b) or
Dodecylbis-(ethyleneoxy) acrylate (5c) or
Dodecyltris-(ethyleneoxy) acrylate (5d) or

1577
Poly(propylene oxide) methacrylate (6)
 1578
Amphiphilic

1. Copolymer of AM with [104,244,245]

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

A monosubstituted monomer derived from 4,4 -azobis(4-cyanopentanoic acid, ACVA), R1 = A or
A disubstituted monomer derived from 4,4 -azobis(4-cyanopentanoic acid, ACVA), R1 = B
2. Terpolymer of AM and DHAM with
A monosubstituted monomer derived from 4,4 -azobis(4-cyanopentanoic acid, ACVA), R2 = C

Model polymer

Copolymer of (AA, R1 = H) or (MAA, R1 = CH3 ) with 2-(1-naphthylacetyl)ethyl acrylate (NAEA) or [246,247]

2-(1-naphthylacetamido)ethyl acrylamide (NAEAm)

Model polymer

Copolymer of AM with N-[(1-pyrenylsulfonamido)ethyl]acrylamide (APS) [110,111]

Table 1 (Continued)

Polymer Structure References

Model polymer

Terpolymer of AM and AA with N-[(1-pyrenylsulfonamido)ethyl]acrylamide (APS) [177]

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

Model polymer

Terpolymer of AM and SA with [(1-naphthyl)methyl]acrylamide (NMA) or APS [178,179]

Model polymer

Copolymer of N-isopropylacrylamide (NIPAM) with N-[4-(1-pyrenyl)butyl]-N-n-octadecylacrylamide [235]

1579
1580 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

Fig. 9. Thermal induced micro-domains [151].

Fig. 10. Schematic presentation of micellar copolymerization [88,135].

Reproduced with permission from [88] 1993, ACS Publishing.

monomers per micelle (NH ) [88,109,134,175,258,276]. It
was first thought that the solubilization of the hydrophobic
monomer in a surfactant micelle, would cause an increase
in the incorporation rate of the hydrophobic monomer
(into the polymer backbone) [109,174]. A NH increase will
change the randomness, i.e. the regularity of the num-
ber of hydrophobic units incorporated in the polymer as a
function of time [109,174]. However two studies [109,277]
demonstrated that by using a disubstituted acrylamide as
the hydrophobic monomer no drift in copolymer com-
position was observed. Therefore, according to the study
[109], the previously thought dissolution of the hydropho-
bic monomer in the surfactant micelle no longer holds
true. The observed behavior can be then attributed to
the difference in polarity between the bulk and micel-
lar phase, which modifies the reactivity of hydrophobes
[109]. Micelle copolymerization can also be used to synthe-
size a more randomly distributed copolymer. This can be
achieved by using a molar ratio where approximately one
hydrophobic unit is solubilized in one micelle [138,275].
Micellar copolymerization remains the most used
method for synthesizing HMPAM [135]. Nevertheless,
another method that is closely related to the micel-
lar copolymerization technique seems promising, but it
involves using a micelle-forming polymerizable surfac-
tant [114,115,178,179,220,278–280]. Although identifying
a correct polymerizable surfactant for the desired molecu-
lar structure is difficult, the technique offers the advantage
that purification (i.e. removal of surfactants as is the case
with micellar copolymerization) of the reaction mixture
no longer would be required. Yet another method, which
recently has been developed, is template copolymerization.
The structure of the copolymer is defined by the template
that is used. A schematic presentation illustrating the tem-
plate copolymerization is given in Fig. 11.
The advantage of this technique with respect to the
other ones is that the block-like distribution of hydrophobic
groups is better controlled. According to several differ-
ent studies [281–285] a longer sequence distribution of
hydrophobic groups can be achieved with this technique.
The molecular weights of the polymers influence their
behavior in solutions. The molecular weight of HMPAM
remains difficult to determine since intramolecular associ-
ations still exist even at very low polymer concentrations.

Fig. 11. Schematic presentation of the template copolymerization technique.

 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
Nevertheless, several different methods have been devised.
These include using the Mark–Houwink–Sakurada rela-
tion for polymers dissolved in water [110,113,114] or
unmodified polymers in the exact same conditions as their
modified analogues [103,229,230,286,287]. However, all
these methods introduce errors in the molecular weight
determination and it would be better to find a suitable sol-
vent in which the polymer is molecularly dispersed [135].
Several authors reported on formamide as a suitable sol-
vent for the molecular weight determination and measured
it by using light scattering experiments [88,109,174].
Another popular strategy to increase the thickening
ability of polyacrylamide polymers is related to the pres-
ence of electrical charges along the backbone. Indeed,
many different polyelectrolytes based on acrylamide have
been synthesized. These polyelectrolytes can be divided
into polyampholytes which include zwitterionic backbone
polymers 9–11, having positive and negative charges in
separate building blocks in the backbone, and zwitterionic
monomers 3–8 having positive and negative charges in the
same building block, and traditional polyelectrolytes 1 and
2. The charges can be induced by controlling the pH of the
subsequent polymer solution when, for example, AA is used
as a co-monomer. In all cases it is reported that the solu-
tion viscosity is a function of the chemical structure and
the solution characteristics (i.e. ionic strength).
From the discussion on the polymers 1–11 one can
conclude that there are many different advantages of incor-
porating electronic charges into water-soluble polymers.
One such advantage is the ability to control the interaction
between the polymer chains by altering the pH or ionic
strength of the polymer solution. Another is the solubil-
ity in water, which makes the corresponding solutions less
sensitive, in terms of viscosity, to the external temperature.
On the other hand if water-soluble polymers are
required whose rheological properties are indepen-
dent of the pH, polyelectrolytes bearing only one type
of charge can be used [201]. For applications where
concentrated salt solutions are used (such as EOR),
polyampholytes are suitable. They have been demon-
strated to display an enhancement in the solution viscosity
upon addition of low molecular weight electrolytes
[197,201,204,209–211,288,289]. This behavior has been
attributed to the shielding of intramolecular Coulom-
bic attraction rather than the intermolecular interactions.
With careful molecular design water-soluble polymers
containing electronic charges can be synthesized exhibit-
ing the required rheological behavior. Peiffer and Lundberg
[289] reported that in order to control the physical prop-
erties of the zwitterionic polymers it is crucial to separate
the oppositely charged monomers using neutral ones.
Derivatives of polyelectrolytes have been investigated
with amphiphilic (hydrophobic) moieties incorporated
along with charges, either positive or negative. These acry-
lamide based amphiphilic polyelectrolytes, 12–17, have
been synthesized by many different research groups in
search for better thickening polymers in different appli-
cations.
Polymers where both charges are incorporated along
with hydrophobic groups have also been studied. These
polymers can be classified as zwitterionic amphiphilics,
1581
19–21. The properties of the subsequent polymer solutions
can be tailored by careful design of the polymer structure
and composition. The polymers can be designed to be salt-
tolerant or responsive to changes in the salt concentration
or ionic strength.
Amphiphilics, 23–28, without electronic charges have
been studied extensively for their salt-tolerance. Addition
of salt will not affect the viscosity of the polymer solu-
tion since its thickening capability arises from hydrophobic
associations and not from electronic interactions.
The polymers 29–33 have been synthesized in order to
enable fluorescence studies of hydrophobically associating
polymers. This technique allows studying the associating
behavior of these polymers through their photo-physical
behavior in response to changes in the system. It has
been demonstrated that polymers of acrylamide containing
pyrene functionalities exhibit increased in excited-state
dimer (excimer) formation and viscosity [110,111,179].
Variation in type of polymers causes different behavior
of the subsequent polymeric solutions. However there are
other parameters that also affect the structure and associ-
ations of the polymer solution: the chemical structure, the
synthesis method, the temperature, the type and concen-
tration of salt and the pH (ionic strength). The following
discussion summarizes the effect of these parameters.
3.1.1. Chemical structure
Generally speaking the first macroscopic effect of the
polymer chemical structure is observed from the cor-
responding solubility in water. Indeed, the solubility of
polymer 3 is dependent on the level of AMPDAPS monomer
incorporated [196]. This has a clear influence on the vis-
cosity of the solution [196] as observed for polymer 5 as
function of the AMPDAE and AMPDAH monomers incor-
poration level [199,200]. The same considerations hold for
polymer 6 as function of the monomer composition (in
this case AMPDAPS and AA) [201] as well as polymer 8
as function of the charged monomer (DADPMA) intake
[203]. The same can be said for polymer 19 where phase
separation is observed at low incorporation levels of the
DAMAPS monomer. These trends are easily understand-
able on the basis of simple considerations regarding the
overall polarity of the polymeric chains. However, in con-
trast to this, polymer (8) is no longer soluble in water
when it contains more than 1 mol% of DADPMA. In a similar
example, McCormick and Johnson [208] observed hydrogel
formation when the incorporation level of charged groups
surpassed 1 mol% in polymer 10. Similar to polymer 8, poly-
mer (10) forms hydrogels and is no longer water-soluble
above 1 mol% incorporation of the charged groups. The car-
boxylate groups lead to strong ionic interactions which
prevents the dissolution of polymer 10 [208]. It seems thus
that the nature of the charge (e.g. carboxylate versus, sul-
fonate anion in Table 1) exert a clear influence on the
association behavior and ultimately on the solubility of the
polymer. This phenomenon is never observed in the case
of a zwitterionic backbone. Indeed, at low incorporation of
either monomer, AMPDAC or NaAMPS, in the correspond-
ing copolymer (polymer series 11) classic polyelectrolyte
behavior is exhibited by the solution. However, poly-
meric solution employing polymers containing equimolar
1582 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
amounts of the AMPDAC and NaAMPS monomers display
high salt tolerance [209]. A similar behavior is observed
when, instead of AMPDAC, AMPTAC is used as the sec-
ond monomer [211]. Similar to polymer 11, polymer 19
exhibits classic polyelectrolyte behavior when the incor-
poration rate of DAMAPS is below 40 mol% [226]. However,
in dilute solutions of polymer 19 (both DADMAC-1 or 2
copolymer) primarily intra-molecular hydrophobic associ-
ations are present [228].
The presence of hydrophobic groups along the polymer
backbone results generally in the formation of micro-
domains. Important parameters for association behavior
of the polymers are the distribution of the hydrophobic
groups and their hydrophobicity. As mentioned before,
a block-like distribution of the hydrophobic groups will
lead to stronger associations compared to a random dis-
tribution. The surfactant to micelle ratio (SMR) during
polymerization affects the distribution of the hydrophobic
groups. At low SMR the block-like distribution is favored
while at high SMR a random distribution is preferred
[175]. Polymers 13, 14 (synthesized using a high SMR)
and 17 (using solution polymerization) are classic exam-
ples of low level association due to random distribution
of the hydrophobic groups [156,175,220] while polymers
14 (synthesized with a low SMR), 17 (using micellar poly-
merization) and 30 are classic examples of a block-like
distribution [111,175,220]. Although the SMR has been
identified as an important parameter for the observed
association behavior, its effect on the composition and
molecular weight of the polymer is minimal as demon-
strated with polymer 31 [177].
The presence of hydrophobic groups suppresses the
solubility of the polymer. Following this, it is easy to
understand that increasing the fraction of the hydrophobic
groups above a certain percentage will lead to solubil-
ity issues, i.e. the polymer is no longer water-soluble.
This has been demonstrated with polymer 24 where a
water insoluble polymer was obtained using DiC8 AM as
the co-monomer above an incorporation rate of 1.2 mol%
[237].
Increasing the hydrophobicity of the hydrophobic
groups will impart better thickening capability of the poly-
mer as demonstrated with the polymers 12, 15, 17, 18, 23,
24 and 27 (2a, 2b, 3a–c and 4a–d). It has been demonstrated
that only a fraction of the hydrophobic groups contribute
to the formation of micro-domains which is affected by the
hydrophobicity of the groups and the incorporation rate
[290]. The hydrophobicity of the groups can be increased
by increasing the length of the groups [103,220,237], using
twin-tailed hydrophobes instead of single tailed groups
[185,218] or using fluorocarbons instead of hydrocarbons
[212,223,242,269]. The critical polymer concentration at
which hydrophobic associations (critical association con-
centration, CAC) arise is reduced compared to classic
associating polymers [218]. These trends can be explained
by the stronger interactions between the hydrophobic
groups due to their increased hydrophobicity. The length
of the hydrophobic groups is important for association
where a short hydrophobe will not lead to association as
demonstrated with polymer 24 using DiC3 AM as the co-
monomer [237]. Increasing its length, by using DiC8 AM as
the co-monomer, does impart associations [237]. However,
in contrast to this, increasing the hydrophobicity too much
will lead to insolubility of the polymers as observed with
polymer 15 using longer twin-tailed groups than DiC12 AM
[218].
The presence of spacers, i.e. small chains linking the
hydrophobic groups to the backbone, affects the associ-
ation behavior of the polymers markedly. Increasing the
length of the spacers allows for easier movement of the
hydrophobic group in solution which in theory should
lead to easier formation of micro-domains and thus inter-
molecular association is favored. This is demonstrated
with polymer 13 [216] (DemMA series). The association
behavior of the polymer is not affected by the type of
co-monomer that is used as long as the length of the
spacer is large enough (in this case a length of 25 EO
moieties). At intermediate lengths (2 or 6 EO moieties)
this is no longer true as demonstrated with the same
polymer backbone [216]. With NaA as co-monomer the
network formation was favorable at shorter EO spac-
ers while just the opposite behavior is observed with
NaAMPS as the co-monomer. The authors [216] attribute
this difference to the stronger tendency of intermolecular
association for the NaA containing copolymer. The pres-
ence of a charged group further away from the polymer
backbone will disrupt the hydrophobic associations to a
greater extent than when the charged group is closer to
the polymer backbone [229]. The NaAMPS co-monomer
places the charged group further away from the backbone
thus leading to a stronger disruption of the hydropho-
bic group association at similar length EO spacers. This
behavior has been identified for the aforementioned poly-
mer 13 and for polymer 20. In addition, charge density
of the polymer affects the association behavior. Using
low charge density co-monomers (carboxylate anions)
will display stronger association above the CAC due to
less interference with the hydrophobic associations, while
sulfonate anions (higher charge density than carboxy-
late anions) will display the opposite behavior. Polymers
bearing high charge density groups are more suscepti-
ble to screening effects in the presence of low molecular
weight electrolytes and will therefore be less responsive
at high electrolyte concentration or low pH. The poly-
mer series 21 is a classic example of this [230]. When
using 3 co-monomers the incorporation level of charged
species will also affect the association behavior of the poly-
mer. At low incorporation levels of charged species no
suppression of the hydrophobic associations is expected.
However, at high incorporation levels the interference with
the associations is expected to be significant. This was
demonstrated using the polymer series 14. The polymers
with 9 or 21 mol% AA display intermolecular hydrophobic
associations at low pH (<5), and in the presence of NaCl.
However, polymers with 37 mol% acrylic acid do not dis-
play this behavior, not even in de-ionized water and low
pH [176].
A peculiar behavior, in the context of EOR, is the tem-
perature stability of polymers. It has been demonstrated
that by using phenyl containing moieties as co-monomers
increases the stability of polymer 25 (PMAAM) against high
temperatures [239].
 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
Fig. 12. Schematic model structure of HMPAM.
Reproduced with permission from [291] 1991, ACS Publishing.
3.1.2. Rheological properties
Hydrophobic interactions confer HMPAM interesting
rheological and solution properties. Leibler et al. [291]
proposed the “sticky reptation” model, which explains
the complex viscoelastic behavior [112,257,258,292] of
HMPAM polymers. The authors proposed a schematic
model structure where a hydrophobic containing chain
and the hydrophobic interactions between the chains’
hydrophobic groups and other chains in the vicinity are
contained in an imaginary tube (Fig. 12).
According to the model the HMPAM polymer chains
form an entangled transient network where entanglements
and hydrophobic interactions are present. The distance
between entanglements is shorter than the one between
hydrophobic groups. Two different relaxation times, a short
and a long one, are predicted for the entangled transient
network. The short one corresponds to residence time of
a hydrophobic group in a hydrophobic micro-domain and
the long one corresponds to the time a chain takes to rep-
tate outside its tube.
In the dilute region (at low polymer concentration)
intramolecular associations dominate [108]. The hydro-
dynamic volume is reduced and therefore the viscosity
of the subsequent polymer solutions. When the polymer
concentration is increased the solution ideally moves to
the semi-dilute region where intermolecular associations
dominate [107,108,293]. This leads then to network-
like formations (transient network) which substantially
increases the viscosity of the solution [107,108,293].
Many publications discuss the complex nature of the
rheology of polymer solutions of hydrophobically mod-
ified polyelectrolytes. It has been demonstrated that all
the types of non-Newtonian rheological behavior exist
for these polymer solutions, i.e. pseudoplastic; pseu-
dodilatant; thixotropic; and rheopectic. Application of
shear will, in classical pseudoplastic polymeric solu-
tions, disrupt the hydrophobic associations, which leads
to a reduction in viscosity [88,92,103,109,132]. How-
ever this process is reversible, i.e. when the shear is
removed the hydrophobic groups will form new associa-
tion thus returning the viscosity of the solution up to its
1583
original value [88,92,103,109,132–134,136,138,139,242,
257,278,293].
Some associative polymeric solutions display pseudodi-
latant behavior, i.e. increase in viscosity with increasing
shear rate [109,134,220,258,260,293,294]. According to
several studies [109,134,220,295,296] this behavior can be
interpreted as a balance between intra- and intermolecular
associations. Above a given shear rate the intramolecu-
lar associations are disrupted and the polymeric chains
are extended, which leads to more intermolecular asso-
ciations [220]. A later study [258] demonstrated that the
pseudodilatant behavior arises slightly above the crossover
concentration (C*), which is the overlap concentration of
the polymer chains. Increasing the polymer concentration
will lead to a polymeric solution that does not display pseu-
dodilatant behavior [109,134,258,297]. The pseudodilatant
behavior of the polymeric solutions is followed by the
pseudoplastic behavior discussed earlier. Although many
authors have demonstrated the pseudodilatant properties
of HMPAM solutions, it has to be mentioned that there are
differences in the observed behaviors. The most important
one being that polymers produced by post modification
only display the pseudodilatant behavior in the presence
of salt [293,294] while polymers produced using the micel-
lar copolymerization technique display the pseudodilatant
behavior also in water [109,134,220,258,260]. However,
no clear explanation for this observation has been given
yet. As mentioned before, the type of distribution of the
hydrophobic groups has a pronounced effect on the type of
rheology that is subsequently observed in solution. By post
modifying the polymers the distribution of the hydropho-
bic groups would be different since little control is present
on which functional group is modified. The distribution of
the hydrophobic groups is similar to block-like distribution
obtained with micellar copolymerization.
Thixotropic and rheopectic (anti-thixotropic) behavior,
as mentioned before, has been observed. The viscos-
ity against shear rates curves obtained under increasing
and decreasing shear rates are not superimposable
[88,103,175,257]. Thixotropic solutions display a peculiar
behavior where the viscosities along the increasing shear
1584 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
Fig. 13. Counterion mediated interpolymer associations.
Reproduced with permission from [214] 2005, ACS Publishing.
rate curve are all higher than those along the decreasing
shear rate curve, i.e. the viscosity decreases with time at
a constant shear rate. The application of shear disrupts
the hydrophobic associations, both intra- and interchain,
which need time to re-associate in order to recover the
enhanced viscosity. In the semi-dilute region interchain
associations dominate, as mentioned before, and there dis-
ruption by shear will lead to a significant loss in viscosity
[257]. However as the viscosity is recovered, the shear
induced reduction in viscosity is not due to polymer degra-
dation [88]. Polymers prepared using the heterogeneous or
homogeneous technique do not display this behavior [88].
Rheopectic solutions display the opposite behavior, i.e.
the viscosities along the increasing shear rate curve are all
lower than those along decreasing shear rate curve (the
viscosity increases with time at a constant shear rate). This
behavior involves the instant recovery of the hydrophobic
associations after the application of shear and the enhance-
ment of these hydrophobic associations, which explains the
enhanced viscosity [103,175].
3.1.2.1. Effect of inherent parameters. As mentioned
before, spacers between the hydrophobic group and the
hydrophilic backbone can enhance the solution viscosity.
Increasing the length of the spacer will lead to a better
enhancement of the solution viscosity. A classic example of
such behavior is polymer 13 (NaAMPS as the co-monomer)
[215]. A subsequent study [214] demonstrated that,
depending on the incorporation rate of the DEmMA, a sig-
nificant increase in solution viscosity is obtained above the
critical overlap concentration. The authors hypothesized
that the additional increase in solution viscosity is due
to the simultaneous interactions of countercations with
the EO spacers via coordination and with the polyanion
via counterion condensation. A schematic presentation
illustrating this behavior is given in Fig. 13.
It has been demonstrated that the responsiveness of the
polymer solution is more pronounced when a longer spacer
is used. A study of Kathmann et al. [199] demonstrated that
using three methylene groups as spacers increased the pH
responsiveness of the polymer solution compared to when
only one methylene unit is used. The pH responsive behav-
ior of the polymers can also be tailored by molecular design
of the polymer. The ampholytic polymer 7 represents such
a polymer where by smart design different behavior is
achieved as a result of changes in the pH. The polymer
(7) undergoes a polyanion → polyzwitterion → polycation
transition as the pH decreases [202].
The shear rate for the onset of pseudoplastic behav-
ior and the viscoelastic properties are dependent on the
strength of the hydrophobic micro-domains. The strength
depends on the aforementioned hydrophobicity of the
groups. Increasing the hydrophobicity of the groups, i.e.
increasing the length of the groups [220,267], the length
of the hydrophobic segment [220], using twin-tailed rather
than single tailed groups [185] or fluorocarbons instead of
hydrocarbons [298], result in a reduction of the shear rate
for the onset of pseudoplasticity and an enhancement of
the viscoelastic properties. A classic example of a polymer
whose shear rate for the onset of pseudoplasticity reduces
with increase in the hydrophobicity of the groups is poly-
mer 15 [185].
The rheological properties of HMPAM can be, as men-
tioned before, explained by the balance between intra- and
intermolecular hydrophobic associations. The copolymer-
ization process affects the distribution of the hydrophobes
(vida supra). With the preference being intermolecular
associations, an enhancement in the solution viscosity is
obtained whereas with intramolecular associations the
exact opposite is observed [110,111]. Polymers 16 and 29
are classic examples of polymers with an enhanced solu-
tion viscosity due to their preference for intermolecular
association.
The position of the hydrophobic groups along the back-
bone is important [245]. From a chemical point of view
the amount of hydrophobic groups present in the polymer
should have an optimum. If the concentration is low, no
association will arise, while, if too high, solubility issues
play a crucial role. However it is demonstrated that plac-
ing the hydrophobic group (polymer 24) at the ends of
the polymer is the optimal configuration for obtaining the
highest solution viscosity [245]. According to the authors
the placement of hydrophobic groups along the back-
bone of the polymer leads to a polymer with a much
more compact structure in solution compared to when
the hydrophobic groups are placed at both ends. However
when combining the two extremes (telechelic with mul-
tisticker) it was demonstrated that the highest thickening
capability, i.e. solution viscosity against polymer concen-
tration can be obtained [104,245]. The critical polymer
concentration for the onset of hydrophobic associations
depends on the placement of the hydrophobic group [104].
For a telechelic polymer with hydrophobic groups at both
ends and a polymer with hydrophobic groups at both ends
and along the backbone the critical polymer concentra-
tion for the onset of hydrophobic association is the same
whereas for a multisticker polymer with only hydrophobic
groups along the backbone the concentration is higher.
The same kind of consideration, namely strong depen-
dence of the rheological behavior from the chemical
structure is applicable for fluorine containing polymers.
Indeed, polymer 18 displayed shear thickening, which
according to Chang and McCormick [228] depends on the
molecular structure of the copolymer. Increase in the incor-
poration rate of the hydrophobe from 3 to 10 mol% leads to
a more pronounced shear thickening behavior. However
at an incorporation level of 24 mol% the shear thickening
 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
behavior is significantly suppressed. The shear thickening
is attributed to the breakage of intramolecular hydropho-
bic associations by shear. If the hydrophobic associations
are too strong (as is the case for the latter polymer), the
applied shear cannot break the associations and thus shear
thickening is not observed.
The dependency of the solution viscosity on the
(low molecular weight) electrolyte concentration can be
adjusted as function of the chemical structure. Indeed, the
salt tolerance of terpolymer 19, 20 was examined using
three different derivatives (NaAMPS, NaAMB and NaA) as
the third monomer. Terpolymers incorporating NaA as
the third monomer displayed the best salt tolerance of
the three different terpolymers [229,230]. The apparent
viscosity (app ) of the polymer solution was significantly
higher in high salt concentration solution compared to
the other two terpolymers. The strength of the hydropho-
bic associations depends on the type of groups used. The
terpolymers incorporating carboxylate anions displayed
stronger hydrophobic interactions compared to the poly-
mers with sulfonate anions. In addition, the placement of
the anions is crucial for the strength of the hydrophobic
associations. It was demonstrated that the further away
from the polymer backbone the anions are placed the
weaker the hydrophobic associations will be. This behavior
was attributed by the authors [229] to the interference by
the anions with the hydrophobic associations. In addition
the rheological properties of the polymer solutions depend
on the charge density. Polymers with low charge density
lead to less electrostatic interference of the hydrophobic
associations [230].
The rheological properties of polymer 15, 22 and
24 depend on which hydrophobe is incorporated. Using
disubstituted monomers leads to a more pronounced thick-
ening effect compared to monosubstituted ones. This is
attributed to the proximity of two hydrophobic chains
(higher density of the hydrophobic domains) that leads
to stronger hydrophobic associations [109]. In addition
the length of the hydrophobic block affects the rheologi-
cal properties of the polymer. The longer the hydrophobic
blocks, the stronger the hydrophobic associations will be.
The onset of shear thickening shifts to lower shear rates
as the length of the hydrophobic blocks increases [109].
This behavior is demonstrated using polymer 14 (R3 = 5)
where the thickening capability increases as the hydropho-
bic block increases in length [299].
3.1.2.2. Effect of external parameters. For neutral associa-
tive copolymers it has been demonstrated that upon
addition of salt the viscosity of the solution can be enhanced
[103,108,203]. This behavior of the neutral copolymers is
attributed to a “salting out effect”, which arises due to a
change in the solubility of the hydrophobic units [108].
The solubility of the hydrophobic groups decreases with
increasing salt concentration. This leads to the formation of
aggregates, which enhances the interactions between the
polymeric chains [108]. The intermolecular association is
enhanced leading to a stronger network and thus increased
solution viscosity [217]. Polymer 14 is a classic example of
this behavior [217].
1585
The presence of salt causes a shielding of the electro-
static interactions and thus a collapse of the network with
total loss of the solution viscosity. Polymer 1 is a classic
example of such a polyelectrolyte where phase separation
is observed in the presence of multivalency cations [193].
Polymer 5 displays a similar trend. However, a decrease
in the pH of the polymeric solution (containing salts)
improves the solution viscosity [198] due to the increase
in hydrodynamic volume caused by the protonation of the
carboxylic groups at low pH [198–200].
The effect of salt on polymers bearing charged moi-
eties in combination with hydrophobic groups is peculiar.
Indeed, an increase in the solution viscosity is observed
upon the addition of different salts. The presence of salt
screens the electrostatic repulsion thus suppressing the
disruption of hydrophobic associations by the charged
groups. This allows the formation of a stronger network
through hydrophobic associations [225], i.e. intermolecu-
lar hydrophobic interactions are dominant rather than the
electrostatic repulsions [221], and thus an enhancement
of the solution viscosity. Classic examples of this behav-
ior (vida supra) are the polymers 12 [115], 17 [221] (AA-CN
copolymer, N ≥ 12), 18 [225] and 25 [133,238]. Although
not in the same class of polymer, polymer 4 displays the
same behavior [197]. Another possibility is that the methyl
groups on the AMDAPS monomer induce hydrophobic
behavior of the monomer at higher salt concentration
thereby displaying the aforementioned behavior.
Maia et al. [121] demonstrated that the method of
preparing the HMPAM solutions affects their rheological
behavior in the presence of salt (NaCl). When the polymer,
23 (AM–DiC6 AM copolymer), is dissolved in the salt (brine)
solution (A, Fig. 14) the classical behavior, i.e. reduction in
viscosity with increasing salt concentration, is displayed.
However, if the polymer is dissolved in water first, which
is preceded by the addition of salt, a complete different
solution behavior is observed. Diluting a polymer solu-
tion (no salt) with water and adding salt afterwards (B,
Fig. 14) results in a polymer solution whose viscosity passes
through a maximum with increasing salt concentration. If
the polymer solution (no salt) is diluted with salt water
(C, Fig. 14) the viscosity of the resulting polymer solu-
tion increases with increasing salt concentration. Fig. 14
presents the three different behaviors. This confirms the
non-equilibrium character of these solutions, but a better
explanation has yet to be provided.
It has been demonstrated that the following surfac-
tants interact with different HMPAM polymers and give,
depending on the surfactant concentration, a higher
viscosity [90,92,115,138,173,287,300–302]. The interac-
tion between the polymers 12, 13 (both copolymers),
17 (both copolymers), 18 (DADMAC-1 and DADMAC-2
copolymers), 21 (copolymer AM-C10 AM), 22 (terpolymer
1, R2 = 2), 23 (copolymers AM-EAM, AM-BPAM and
AM-2 or 3 or 4), 27 (6) and 33 with several different sur-
factants (SDS [90,92,120,138,173,212,228,243,301–305],
potassium dodecyl sulfate (KDS) [212], cetyltrimethyl-
ammonium p-toluenesulfonate [CTAT] [305,306],
dodecyltrimethylammonium chloride [DTAC] [290,300],
hexadecyltrimethylammonium [HTAC] [303,304], CTAB
[90,233], trimethyltetradecylammonium bromide [TTAB]
1586 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

Fig. 14. Different behavior of HMPAM solution dependent on the preparation method.
Adapted from Maia et al. [121]. Reproduced with permission from [121] 2005, Wiley VCH.

Fig. 15. Schematic presentation of concentration regions of HMPAM with SDS [92].
Reproduced with permissions from [92] 1992 and [132] 1996, ACS Publishing.

[302], cetyldimethylamine oxide [CDMAO] [90], alkyl-
benzenesulfonates [ABS] [287], Triton X-100 [302],
n-octyl ␤-d-glucopyranoside [OG] [303] and n-octyl
␤-d-thioglucopyranoside [OTG] [303,304]) have been
investigated. The viscosity of the HMPAM solution with
surfactant passes through a maximum, which is always
just under the surfactants’ critical micelle concentration
(CMC) [173]. The increase in viscosity is attributed to the
formation of mixed micelles of surfactant and hydrophobic
regions [92,117,120,154,173,300,301,303,304,307–309].
According to several authors [92,303,304], when adding
surfactant to a HMPAM solution, the surfactant binds to
the copolymeric regions, which leads to preferential inter-
chain micro-domain formation instead of intrachain. A
schematic presentation of this behavior has been provided
by Biggs et al. [92] (Fig. 15).
The surfactant concentration in region I is low. The
surfactant associates in a non-cooperative way with
the hydrophobic groups [92]. However, this is depen-
dent on the type of surfactant. Two different studies
[303,304] demonstrated that the surfactants hexade-
cyltrimethylammonium chloride (HTAC) and SDS bonded
in a non-cooperative way but the surfactants OG and OTG
bonded in a cooperative manner. Winnik et al. [304] con-
cluded that ionic surfactants bind by a non-cooperative
mechanism and neutral surfactants by a cooperative one.
According to another study there are two classes of interac-
tions, which are differentiated by the bridging and viscosity
increase below or above the cmc of the surfactant [90]. In
region II enough surfactant molecules (higher surfactant
concentration) are present to solubilize the hydrophobic
groups more effectively (mixed micelles). The formation of
mixed micelles is the onset of a significant increase in vis-
cosity. Most of the mixed micelles incorporate more than
one hydrophobic region, i.e. a higher degree of overlap or
links between separate chains is achieved. In region III the
surfactant concentration is higher, at or above the cmc,
which results in solubilization of each hydrophobic region
in one micelle. This leads to a reduction in viscosity.
Transition from spherical to rod-like micelles in the
surfactant phase has been observed upon addition of
potassium bromide and hexanol to respectively the
polymer–CTAB and polymer–CDMAO mixture [90,115].
The transition is believed to be due to the gain in free energy
upon addition of the chemicals where the hydropho-
bic groups no longer are exposed to the solvent but
instead are present inside the hydrophobic rods [90,115].
Fig. 16 provides a schematic presentation of the rod-like
micelles.
This transition to the rod-like conformation leads to
more intermolecular bridging and thus enhanced solution
properties. This is evident from the significantly higher
viscosity of the solutions compared to the viscosity of
the individual components [90,115]. Both, rheopectic and
thixotropic, behaviors have been observed for polymer
solutions in the presence of surfactant [92].
 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628 1587

Fig. 16. Schematic presentation of rod-like micelles [90,115].

Using polymer 23 (R2 = 2, 3 or 4 series) Gouveia and
Muller [306] observed a large increase in the solution vis-
cosity upon the addition of CTAT. Adding salt (NaCl) to this
solution leads to a further increase in the solution viscos-
ity of the mixture. According to the authors the worm-like
micelles increase in size by the addition of salt and at high
salt concentration salting out effects arise.
A peculiar behavior is observed for the interactions
between fluoro- and hydrocarbon copolymers 12 and sur-
factants. At low incorporation level of the hydrophobic
groups the interactions with surfactants is selective to sur-
factants with the same chemical nature as the hydrophobic
groups [212].
Different oil reservoirs possess different temperatures.
The polymer solutions that are to be used must be able
to cope with the different temperatures, i.e. no loss of
viscosity with alteration in temperature. The viscosity
of polymeric solutions employing the polymers 10 (ter-
polymer of AM–NaAMPS–AMPDAC) or 12 (Table 1) is
minimally dependent on the temperature in the range
30–60 ◦ C [204,209,210]. In addition polymer 12 displayed
good retention of solution viscosity for a prolonged period
(40 days) [209]. The viscosity of the polymer solution
containing the zwitterionic (monomer) polyelectrolyte,
polymer 4, displays a unique behavior when the temper-
ature is increased. The intrinsic viscosity of the polymer
solution increased (from 6.5 to 8.5 dl/g) when the tem-
perature is increased from 25 to 60 ◦ C [197]. This has
been observed for polymer 14 in the temperature range
of 20–40 ◦ C. According to the authors [217] the increase
can be attributed to the fact that hydrophobic associa-
tions are endothermic in the investigated temperature
range, as hypothesized by McCormick et al. [103]. Using
the latter terpolymers 14 L’Alloret et al. [310] observed
a significant increase in the solution viscosity when the
temperature is increased from room temperature to 80 ◦ C.
In addition the authors demonstrated that the thermoth-
ickening behavior of the polymeric solution is more
pronounced at lower salt concentration and lower shear
rates. The latter effect is also observed with polymer 27
(6) [243] and is attributed to the increase in PPO con-
centration in the hydrophobic micro-domains caused by
an increase in the mobility of the chains at relatively
high temperature. At higher temperatures, the reduction
in viscosity is attributed to the loss in connectivity of
the network due to changes in the hydrophobic micro-
domains. According to the authors the size of the micro-
domains increase at higher temperatures but their number

Fig. 17. Schematic illustration representing the thermally induced conformational changes.
Reproduced with permission from [235] 1991, ACS Publishing.
1588 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
Fig. 18. Schematic presentation of the effect of solution pH on the network structure.
Reproduced with permission from [218] 2001, ACS Publishing.
decreases and causes the aforementioned connectivity
loss.
The viscosity of the AM–AMPDAC copolymers in the
polymer series 1 decreased as expected with increasing
temperature [193]. The same behavior is observed for a
polymeric solution employing polymer 2 [195]. Unlike
polymers 1 and 2, an intriguing property of polymer 4 is
the increase of the intrinsic viscosity with temperature (in
the range 25–60 ◦ C). Another polymeric solution that dis-
plays peculiar behavior with increase in the temperature
is the solution of terpolymer (9, AM–NaAMPS–AMPDAC),
which was minimally dependent on the temperature
[204].
The LCST concept, discussed in the introduction of this
chapter, also applies to polymer 33 where the viscosity
of the solution can increase with an increase in temper-
ature. However, one important finding reported by the
authors [235] is the presence of hydrophobic associations
below the LCST. An increase of the solution temperature
(towards the LCST) leads to disruption of these associations.
However, only for long or high hydrophobicity groups do
the associations arise below the LCST. This behavior was
observed with the amphiphilic polymer 23 (NIPAM-CN AM).
Four decades ago, it was proposed that the LCST should
decrease with the polymer hydrophobicity [311]. However,
the study by Ringsdorf et al. [235] demonstrated that the
proposed trend is not followed when increasing the length
of the hydrophobes in polymer 23 (NIPAM series). This
is attributed to the formation of a micellar structure by
the hydrophobes, which prevents them from contributing
to the LCST suppression. On the basis of this hypothesis,
the authors have proposed a model representing the ther-
mally induced polymer conformational changes for both,
23 (NIPAM series) and 33, polymers (see Fig. 17).
In addition, increasing the temperature from 25 to
55 ◦ C leads to the preferential formation of intermolecu-
lar hydrophobic associations and thus an increase in the
viscosity.
The pH of the polymeric solution also affects the solu-
tion viscosity. The effect on classic polyelectrolyte is easily
understood given the charged nature of the polymers.
Polyanions will have a low viscosity at low pH and high
viscosity at high pH while polycations display the oppo-
site behavior. Polymer 2 is a classic example of a polyanion
where the solution viscosity decreases as the pH of the
solution is reduced. The effect of pH is more pronounced
on polyelectrolyte amphiphilics where the associations are
a balance between hydrophobic and electrostatic interac-
tions. Zhou et al. [225] demonstrated, using polymer 18
(AA series), that increasing the pH from 4 to 5 and from
11 to 12, a significant increase in the solution viscosity
is observed while at a pH between 5 and 11 the solu-
tion viscosity is lower. A similar behavior was observed
for polymer 17 (AA series) although the pH where the
increase in solution viscosity is observed is shifted. The
increase is observed between a pH of 5–6 and 12–13 [221].
Although the effect of pH on polyelectrolyte amphiphilics is
complex (vida supra), the investigation of the polymer net-
work structures of solutions employing polymer 15 using
NRET measurements led to the development of a model
illustrating the effect of the solution pH on the confor-
mation of the polymer chains and their associations [218]
(see Fig. 18).
Increasing the pH will lead in principle to the transi-
tion towards more intermolecular associations rather than
intramolecular. The high degree of ionization (at high pH)
will disrupt the intramolecular hydrophobic associations
causing a rearrangement of the network with a prefer-
ence for intermolecular associations [218]. Amphiphilics
are affected by the solution pH mainly due to the carboxylic
groups of the polymers. Polymer 26 is a classic example
showing what the effect of the pH is on the behavior of an
amphiphilic polymer. The solution viscosity passes through
a maximum as the pH rises from 4 to 12. This behavior is
attributed to two different effects: neutralization of the car-
boxylic groups leading to (1) intramolecular electrostatic
repulsion and thus chain extension and (2) intermolec-
ular electrostatic repulsion leading to disruption of the
intermolecular associations. The first effects dominate at
low pH, the latter one at high pH [240]. However, in con-
trast to this classic polyelectrolyte behavior, increase in the
pH results in the formation of intramolecular hydrophobic
association for polymer 29. The carboxyl groups repel each
other in classic polyelectrolytes to form expanded coils,
however the presence of large hydrophobic groups on the
polymer backbone impart the repulsion between the car-
boxylic groups. The polymer forms a much more compact
structure, which is called a hypercoil [312] (Fig. 19).
The hydrophobic groups associate to form the interior
of the hypercoil, which is surrounded by carboxyl groups.
The same behavior has been observed for polyacids bearing
large hydrophobic groups [95,96]. McCormick et al. [219]
noticed the same behavior for polymer 16. By increasing
the ionization degree of the polymers containing 50 mol%
4-butylaniline (4-BA) the polymers undergo a transition
from closed (intramolecular) associations to open (inter-
 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
Fig. 19. Schematic presentation of a hypercoil.
Reproduced with permission from [312] 1986, ACS Publishing.
molecular) associations. If the 4-BA content is 70 mol%
only intramolecular associations are present at all ioniza-
tion degrees. Unlike polymer 16 and 29 no intermolecular
hydrophobic associations could be detected for polymer 31.
This is attributed to the high number of carboxylate units
at high pH which will disturb the water structure to such
an extent that the driving force responsible for hydropho-
bic associations is suppressed. At low pH, intramolecular
hydrogen bonding stabilizes intramolecular hydrophobic
associations thus excluding intermolecular association.
The transition from closed (intramolecular) to open (inter-
molecular) associations has been confirmed using the
model polymer 32. This transition, which is triggered by
changes in the pH and salt concentration can be viewed
as a molecular level event instead of a macroscopic phe-
nomenon [178]. A schematic presentation of this behavior
has been provided by Kramer et al. [179] (see Fig. 20).
Although a transition arises for polymer 19 with
changes in the ionic strength and/or pH, the restructuring of
Fig. 21. Schematic presentation illustrating the effect of pH and ionic strength.
Reproduced with permission from [226] 2000 and [227] 2000, ACS Publishing.
1589
Fig. 20. Schematic presentation of transition to intramolecular associa-
tion.
Reproduced with permission from [179] 1995, ACS Publishing.
the polymer is different. Two models have been proposed
by the two studies [226,227] illustrating the effect of the
ionic strength and pH on the structure of polymer 19 that
is obtained (see Fig. 21).
Indeed, for classic polyelectrolytes, increasing the ionic
strength of the solution (i.e. increasing the salt concentra-
tion) will lead to a decrease in the solution viscosity due to
screening effects. However for polymer 9, which bears both
electronic charges, a peculiar behavior is observed where
the intrinsic viscosity increases with increase in the ionic
strength [205,206].
3.2. Hydrophobically modified ethoxylated urethane
(HEUR)
The interest in HEUR focussed on fundamental research
[313] and commercial applications in paint formula-
tion [314,315], paper coating [314,315] and shampoo
1590 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
Fig. 22. Chemical structure HM PEO.
formulation [314,315]. Their use as model compounds can
significantly increase the scientific understanding of asso-
ciating polymers. Table 2 presents an overview of the
published systems with the corresponding chemical struc-
ture.
HEUR polymers are prepared by chain extension of
poly(ethylene oxide) (PEO) oligomer with a narrow molec-
ular weight distribution (MWD) using di-isocyanate and
end-capping with a hydrophobic group [105]. HEUR poly-
mers can be categorized into two main classes: step growth
(S-G) HEUR and uni-HEUR. The differences between the
two classes relates to the synthesis method and the cor-
responding MWD of the product [336]. The S-G HEUR
involves a procedure where PEO (of a given Mw) is reacted
with a large excess of a di-isocyanate agent to produce
a precursor which contains isocyanate functional groups
at both ends. This precursor is subsequently reacted with
a hydrophobic group to end-cap both ends yielding a
telechelic polymer. This procedure leads to a HEUR poly-
mer displaying a broad MWD. The procedure for uni-HEUR
involves the direct addition of a mono-isocyanate contain-
ing a hydrophobic group to the PEO. To this a hydrophobic
group is added. The resulting polymer has a relatively nar-
row MWD, which is related to that of the parent PEO. The
chemical structure of a hydrophobically modified PEO is
given in Fig. 22.
HEUR polymers are designed to be end-capped at both
ends with a hydrophobic group. However it has been
demonstrated that, in practice, a significant fraction of
these polymers is end-capped at only one side [337]. The
polymers usually comprise a mixture of telechelic polymer
and nonionic surfactant [125].
In most cases long chain alcohols [105,122,322,324,325]
are used as hydrophobic groups although other types of
hydrophobic groups have been investigated. These include
fluorocarbon containing hydrophobes [186,329–331],
amine containing hydrophobes [122], alkyl groups
[124,128,170,316,327] and alkoxy groups [129,318,319].
Combinations of telechelic and internal hydrophobes [122]
and comb-like structures using a long chain 1,2-diol [125]
have been investigated.
As mentioned earlier an isocyanate agent is used
in the synthesis. Different isocyanate agents have
been used such as isophorone di-isocyanate (IPDI)
[122,125,129,186,318,319,329–331,338], dicyclohexyl-
methane di-isocyanate [322,324,325], octadecyl (alkyl)
isocyanate [317,323,339] and different polyisocyanates
[317,339].
Differences in the synthetic procedures and the used
hydrophobic groups clearly result, as discussed below, in
different structures of the corresponding water solutions
and their rheological behavior.
The physical structure that telechelic polymers attain,
when solubilized in an aqueous environment, was eluci-
dated using fluorescence studies. In principle rosette-like
[124,126,318,319,328] aggregates are formed with diam-
eters in the nanometer range resembling star polymers
[340,341]. The formation of these structures starts above
the critical micelle concentration (CMC) [124]. The rosette-
like structure comprises an inner core rich in hydrophobic
groups (ranging from 4 to 20 hydrophobic groups) and a
corona composed of the hydrophilic PEO chains (approx-
imately 5–10 looped chains) [130,318,319,342]. The
number of hydrophobic groups present in the hydropho-
bic core depends on the type of group used [326]. The
number of hydrophobic groups in the inner core and
the structure of the corona are independent of polymer
concentration [318,319], only the number of rosettes is
affected by the polymer concentration. Although the exact
dimensions vary with the polymer molecular structure,
the polymers 35, 36, 43 and 44 all were demonstrated to
form the aforementioned structures in an aqueous solu-
tion. Fig. 23, provided by Xu et al. [343], shows the micelle
structures and the effect of polymer concentration on the
conformation of the polymer (for polymer 36, AT 22-
3).
Several other publications [105,126,329,338] provided
similar schemes illustrating the different concentration
regimes.
Aside from the independency of the structures on con-
centration, the type of end group is another parameter
that does not affect the network structure. According to
Fonnum et al. [328], only the relaxation time of the net-
work depends on the end group as observed with polymer
45 (1–6).
The rosettes can be bridged by polymeric chains, at
higher concentration, leading to a network as displayed
in Fig. 23. The higher the tendency towards bridging, the
more stable the network will be. The bridging is affected
by the polymer molecular structure. Xu et al. [343] have
demonstrated that the comb polymer 36 has a much
higher fraction of bridging chains and a lower fraction of
loop chains when compared to the telechelic analogues.
When investigating the structures of HEUR polymers,
polymer 38(2) containing only one hydrophobic group, a
peculiar behavior is observed. A smaller hydrophobicity
group (C6 F13 ) leads to dimer formation whereas a larger
hydrophobicity group (C8 F17 ) leads to the formation of
micelles (Fig. 24) [189].
For HEUR polymers hydrophobic associations start
at very low polymer concentration (as low as 10 ppm).
Although the exact critical concentration for the onset of
hydrophobic association varies, the solutions employing
polymers 39, 43 and 44 have a critical concentration in
the same range [125,327]. Most of the HEUR polymers in
Table 2 contain urethane linkages. A study by Alami et al.
[344] demonstrated that at low polymer concentration
the presence of urethane linkages dramatically influence
the initial association and the clouding of the polymer
in water. HEUR polymers containing urethane linkages
will form aggregates sooner than their analogues without
Table 2
Structure of different water-soluble polymers, HEUR.

Polymer Structure References

Polyethylene oxide end capped at both sides with dodecyl groups. [316]

Polyethylene oxide end capped at both sides with different alkane hydrocarbon [89,317]
groups (R) employing different diisocyanates moieties (DI).
Given the amount of different reagents used we refer to US Pat. 4,079,028 [317] for the
complete list of reagents.

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

Polyethylene oxide end capped at both sides with an hexadecyl group: [318,319]

AT 22-2, y = 4
AT 22-3, y = 6
AT 107, y = 3
AT 67-3, y = 1
IPDU = isophorone diurethane

Polymers based on ethylene oxide using different hydrophobic groups and different [122]
structure. Either end capped (traditional HEUR polymers, 1) or the hydrophobic end
groups are separated by oxyethylene groups around an internal hydrophobe, 2–4.

1591
 1592
R = different amine and alcohol containing groups

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

Polymers based on ethylene oxide using different hydrophobic groups and different [189,320]
diisocyanate groups. The polymers are either end capped at both sides with internal
hydrophobic groups.

R = C6 H13 , C8 H17 , C12 H23 , C14 H29 and C18 H37

Polymers based on ethylene oxide: [125]

Comb-81, w = 1, y = 2 and z = 3
Comb-82, w = 1, y = 2 and z = 6
Comb-83, w = 1, y = 2 and z = 9
IPDU = isophorone diurethane
Table 2 (Continued)

Polymer Structure References

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

Polymers based on ethylene oxide: [321]

A: ethylene oxide-alkylglycidyl ether) copolymer (EO-AGE)

B: ethylene oxide-3,3-dialkoxymethyl)propyl glycidyl ether) copolymer (EO-DAGE)
C: poly(methyleneoxide-alt(PEO)polyalkyl-glycidyl ether (MO-PEO-PAGE)

Polymers based on ethylene oxide: [124]

AT18-31, n = 230, DI = 1 and R = 4

AT18-13, n = 90, DI = 1 and R = 4
AT18-19, n = 140, DI = 2 and R = 4
AT15-19, n = 140, DI = 2 and R = 5
AT17:1-19, n = 140, DI = 2 and R = 3
DI = diisocyanate

1593
 1594
Polymers based on ethylene oxide, end capped at both sides with: [322–325]

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

Dodecyl alcohol (N = 12) or
Cetyl alcohol (N = 16)

Polymers based on ethylene oxide, end capped at both sides with hexyl (N = 5), octyl [188,326]
(N = 7) or dodecyl (N = 11) using either hexamethylene diisocyanate (HDI) or
bis(4-isocyanateocyclohexyl)methane (H12 MDI) as the diisocyanate group.

1: HDI with hexyl, octyl or dodecyl

2: H12 MDI with hexyl, octyl or dodecyl
or
3: HDU with hexadecyl endgroups

Polymers based on ethylene oxide, end capped at both sides with n-hexadecyl groups. [327]
Table 2 (Continued)

Polymer Structure References

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

Polymer based on ethylene oxide, end capped at both sides with different alkyl groups: [328]

1: R1 = C17 H35 , C14 H29 or C11 H23

R2 = C6 H12
2: R3 = C16 H33 , C13 H27 , C10 H21 , C8 H17 or CH3
R4 = C13 H22
3: R5 = C9 H19 C6 H4 (OCH2 CH2 )n , n = 2, 4, 7, 10, 15
R6 = C13 H22
4: R7 = C18 H37
R8 = C7 H6 , C6 H12 , C13 H22 or C12 H24
5: R9 = C18 H37
6: R10 = C17 H37 or C10 H21
R11 = C6 H12 or C13 H22

1595
 1596
Polymer based on ethylene oxide, end capped either at one side (1) or at both sides (2) [187]
with octadecyl groups (1) or with nonylphenol (2) groups:

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

n = the number of oxyethylene units
m = the number of hydrophobes per chain
1: n = 182, 331, 531 or 663
m (182) = 1.6, 1.7 or >2.0
m (331) = 1.4, or >2.0
m (531) = 1.2, or >2.0
m (663) = >2.0
2: n = 182, 331, 531 or 663
m (all cases) = 2.0

Polymers based on ethylene oxide end capped at both sides with fluorocarbon [329]
hydrophobes:

C6 F-35K, n = 6 or
C8 F-35K, n = 8

Polymers based on ethylene oxide end capped either at both (1) or one side (2) with [186,330,331]
fluorocarbon hydrophobes.
Table 2 (Continued)

Polymer Structure References

End group: F(CF2 )8 (CH2 )11

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

Polymers based on ethylene oxide end capped either at both or one side with [182,332–334]
fluorocarbon hydrophobes:

H17 –H17 : 1
F8 –F8 : 2, N = 0
F8 H2 –H2 F8 : 2, N = 2
F8 H10 –H10 F8 : 2, N = 10
H18 –H2 F8 : 3, N = 2
H18 –H10 F8 : 3, N = 10
H1 –H2 F8 : 4

Polymers based on ethylene oxide end capped at both ends with pyrene. [335]

1597
1598 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

Fig. 23. Concentration regimes of a telechelic PEO.

Reproduced with permission from [343] 1997, ACS Publishing.

urethane linkages. The polymer series 49 was synthe-
sized with the idea that this would be better model
polymers since no interference by urethane linkages is
present [332]. Indeed, it was already demonstrated by
another study [344] that significant changes in associ-
ating behavior are observed when telechelic polymers
with an ether versus a urethane bond connecting the
hydrophobic groups with the polyethylene oxide chain are
compared.
The association behavior of the polymer in solution
depends on the molecular structure of the polymer. When
Liu et al. [321] investigated polymer 40 a significantly
different association mechanism was observed when com-
paring comb and telechelic polymers. Comb associative
polymers display a more compact structure in compari-
son to the association of equivalent telechelic polymers.
The authors [321] hypothesized, similar to the conclusion
of Jimenez-Regalado et al. [245], that comb associative
polymers favour the formation of intramolecular associ-
ations instead of intermolecular association which occurs
for telechelic polymers.
When using a combination of small spacers between the
end groups and the PEO backbone, internal hydrophobe
phase separation was noted (polymer 37, 2–4). Accord-
ing to the authors [122] this behavior can be attributed
to the dominance of intramolecular hydrophobic associ-
ations. To resolve this, the use of SDS was suggested. The
polymer series 38(1) are prepared by step growth poly-
merization and, as a result, a mixture of components is
obtained [320]. In principle the strength of the network in
solution depends on the type of hydrophobic group used
and the length of the PEO chain. The strength of the network
can be increased by increasing the hydrophobicity of the
end groups. The hydrophobicity can be increased by using
larger sized hydrophobes, using fluorocarbon rather than
hydrocarbons, or by increasing the size of the di-isocyanate
group [124,320,329,330]. An example of such a poly-
mer is polymer 41 where increasing the hydrophobicity

Fig. 24. Dimer and micelle formation for polymer 35 (2).

Reproduced with permission from [189] 1998, ACS Publishing.

Fig. 25. Superbridges, superloops and dangling ends.

 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
of the end group leads to an enhanced network. It was
demonstrated that the thickening efficiency decreased in
the order of octadecyl > pentadecyl > 9-heptadecenyl [124].
The same trend was observed for polymer 43 (2) where
the thickening efficiency decreased in the order of dode-
cyl > octyl > hexyl [188] and for polymer 45 (1–6) [328].
Polymers 46, 47 and 48 (1 and 2) represent polymers with
increased network strength due to the presence of fluoro-
carbons instead of hydrocarbons.
3.2.1. Rheological properties
Several publications presented the rheological proper-
ties of HEUR polymers in aqueous solutions. In aqueous
solution HEUR polymers form transient networks, which
follow a Maxwellian behavior with a single characteristic
relaxation time [89,124,318,328,338,343,345–349]. This
relaxation time was attributed to the residence time of
a hydrophobic end (group) inside a hydrophobic micro-
domain.
At low polymer concentration, no micelles are present
and the viscosity of the solution equals the viscosity of
the solute. Increasing the polymer concentration above
the CMC leads to micelle formation without a significant
increase in viscosity. A further increase in the poly-
mer concentration leads to more micelles. As mentioned
before, these micelles can be interpreted as star-like poly-
mers, which are known to repel each other in good
solvents [89,345–347,350]. However, telechelic micelles
have the possibility of forming bridges between two sep-
arate hydrophobic cores, thus leading to cluster formation
between them [341]. The viscosity of the polymer solu-
tion now changes due to an increase in the hydrodynamic
volume of the micellar clusters formed. Raising the poly-
mer concentration leads to networks (microgels) which
are connected through bridges [351,352]. These microgels
break upon dilution of the polymer solution. Two studies
from the Annable group [89,350] proposed similar network
formation where micelles (or a collection of micelles) are
connected through superbridges and superloops. Super-
bridges connect several micelles in a linear fashion whereas
superloops connect several micelles in a non-linear
fashion, but the start and end of this superloop rest in
the same micelle [89,350]. In addition, dangling ends are
present in the microgels, which are chains with only one
hydrophobic end associated with other hydrophobic enti-
ties (Fig. 25).
By using fluorescence spectroscopy, it has been demon-
strated that a critical association concentration (CAC) exists
for telechelic polymers end-capped with alkyl groups
[89,128] (polymer 34). Above the CAC the viscosity of the
polymer solution increases more sharply with increasing
concentration when compared to polymers lacking the
hydrophobic groups [128].
In HEUR solution the interchange of the bridges con-
necting the micellar clusters is fast at low shear rates,
without breakage by shear [170] and thus no loss of
solution viscosity. Nevertheless, HEUR polymers also dis-
play pseudoplastic and pseudodilatant behavior. Under
steady shear, the HEUR polymeric solutions display a strong
pseudoplastic behavior that is preceded by a weak shear
thickening. The pseudoplastic behavior arises due to the
1599
breakage of the bridges as the shear increases [328]. The
microgels reduce in size and thus also the hydrodynamic
volume leading to a lower viscosity of the solution. As
mentioned before, prior to shear thinning a weak pseu-
dodilatant behavior is observed. At moderate shear the
microgels are deformed, which entails the stretching of
the bridges connecting the microgels [105,318,319,328].
The bridges resist breakage by stretching (up to a cer-
tain point) and therefore induce a shear thickening
[105,318,319]. A further increase in the shear rate leads
to the aforementioned pseudoplastic behavior. Tam et al.
[105] investigated the network structure of polymer 36
(AT22-3) in shear flows and proposed a more refined model
than the one provided by Yekta et al. [338], depicting
the different structures the network attains under shear
(Fig. 26).
As the shear is increased shorter superbridges are
formed but the density of mechanically active, i.e. part
of the polymer network, chains increases. This leads to a
stronger network and thus a higher solution viscosity. A
further increase of shear will lead to the shear thinning
regions. According to the study [105] three different shear
thinning regions can be distinguished for polymer 36, i.e.
regions A, B and C. Regions 1 and 2 are characterized by
a significant loss in viscosity and the difference between
the two is a reduced slope (viscosity versus shear stress
plot) of the latter one. Region 3 is characterized by a large
drop in the solution viscosity with increasing shear. The
difference between regions 1–2 and 3 is the mechanism
causing the loss in viscosity. It was demonstrated that in
regions 1–2 the superbridge network junctions disrupt,
but they rearrange quickly without a loss in the num-
ber of bridges. The reduction in the relaxation time leads
to the reduction in viscosity for regions 1 and 2 given
that the viscosity is dependent on two separate processes
according to the  = G0 equation ( = relaxation time and
G0 = plateau modulus) for a Maxwell fluid [105]. The loss in
viscosity for region 3 is attributed to fragmentation of the
network.
3.2.2. Effects of inherent parameters
Telechelic polymers such as the polymer series 35
display in steady shear a Newtonian behavior up to rela-
tively high shear rates [105]. This is in stark contrast with
polymers bearing hydrophobic moieties distributed along
their backbone, where shear thinning predominates. When
incorporating the hydrophobic group along the polymer
backbone, the thickening capability, i.e. solution viscos-
ity as a function of the polymer concentration, is lower
when compared to telechelic polymer [89]. The comb asso-
ciative polymer 40 is an example of a polymer with less
pronounced increase in solution viscosity when compared
to a telechelic equivalent. However, it must be mentioned
that although both polymers are quite similar, the molecu-
lar weight of the comb type is higher than for the telechelic
one. In addition, it was demonstrated that the distribu-
tion of the hydrophobic groups plays a crucial role in
the observed behavior. When each of the hydrophobic
moieties consist of two hydrocarbon groups the thicken-
ing capability is significantly enhanced. This is similar to
the behavior observed for twin-tailed HMPAM polymer
1600 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
15 [321]. The hydrophobicity of the groups increases and
therefore a stronger interaction gives rise to the observed
enhanced thickening capability. In light of this, the com-
parison between a single comb and telechelic polymers of
polymer 40 is not viable given the low hydrophobicity of
the groups in the comb polymer.
Internal hydrophobes affect the rheological properties
of HEUR solution due to the preference for intramolecular
hydrophobic associations. However, there are conflicting
reports on the effects of internal hydrophobes. According
to Fonnum et al. [328] internal hydrophobes do not affect
the rheology of polymeric solution employing polymer 45.
On the other hand Lundberg et al. [122] concluded that
using HEUR polymer 37 (with an internal hydrophobe in
combination with two terminal hydrophobes) resulted in
a more compact structure due to intramolecular hydropho-
bic associations rather than intermolecular (vida supra).
This leads to a reduction of the hydrodynamic volume of
the polymer chains, and thus a reduction in the solution
viscosity.
The hydrophobicity of the end groups affects the rhe-
ological properties. According to Calvet et al. [330] the
increase in hydrophobicity of the groups leads to an
increase in the lifetime that the hydrophobic end groups
are present in the hydrophobic core. It has also been
demonstrated that the monofunctionalized polymer 48 (2)
displays a marked difference in rheology compared to the
difunctionalized polymer 48 (1) [330]. The concentration
at which the onset of significant (static) viscosity increase
is observed is much lower for the difunctionalized poly-
mer. However, it cannot be concluded that this difference
is only caused by the single end capping since the molecu-
lar weight of the monofunctionalized polymer is half that
of the difunctionalized one.
The rheological properties of a HEUR solution also
depend on the molecular weight of the polymers. In prin-
ciple, the molecular weight of the HEUR polymer has an
optimal intermediate range where the highest thicken-
ing capability can be obtained [331]. The critical polymer
Fig. 26. Model depicting the effect of shear on the network structure.
Reproduced with permission from [338] 1998, ACS Publishing.
concentration for the onset of hydrophobic association
is also affected by the molecular weight of the polymer.
According to Kaczmarski and Glass [187] the increase in
the number of EO units (increase in molecular weight)
promotes the formation of intermolecular associations
and thus increasing the network strength leading to an
enhanced solution viscosity. At low molecular weights, a
reduction in the solution viscosity is observed due to a
reduction in the hydrodynamic volume of the polymer. At
high molecular weights, also a reduction in solution vis-
cosity is observed. This is attributed to the decrease in the
concentration of the hydrophobic groups, which leads to
less hydrophobic micro-domains being formed and thus
a weaker network. Polymers 42, 43, 45 (1–6) and 47 are
classic examples of polymers whose rheological properties
depend on the molecular weight. The molecular weight is
closely related to the PDI. The PDI also affects the rheo-
logical properties of the polymeric solution. A study [325]
compared the thickening capability of the polymers and
found significant differences in the viscosity enhancement
capability. For instance, when a broad MWD polymer is
used twice as much polymer (concentration) is required
to attain the same viscosity of a narrow MWD polymer.
However, the storage and loss moduli were similar despite
the concentration difference. Broad MWD polymers con-
tain small polymer chains of low molecular weight and
these polymers favor the formation of intramolecular
hydrophobic associations. This leads to a weakened poly-
mer network, which reduces the viscosity enhancement
capability.
3.2.3. Effects of external parameters
Interactions between surfactants and HEUR polymers
in solution have been demonstrated by several authors
[127,353,354]. Depending on the concentration of the
surfactant, an increase in viscosity of the solution can
be observed. Interactions between polymers 34, 36 (AT
22-3), 37 (1), 41, 49 and 50 and the surfactants SDS
[124,164,182,335,353–357], DTAB [354], nonylphenol
 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
Fig. 27. Different aggregates formed with the addition of surfactant.
Reproduced with permission from [127] 1996, ACS Publishing.
ethoxylates (NP) with different degree of ethoxylation
[353], polyoxyethylene glycol (C12 E8 , nonionic surfactant)
[127] and polyoxyethylene stearyl ether (C18 [EO]20 ) [358]
have been investigated. The effect of the surfactant has
been summarized by Annable et al. [353] in terms of the
plateau modulus: (1) at low polymer concentration the
plateau modulus is significantly raised using a low to
moderate amount of surfactant, (2) using higher surfactant
concentration leads to a monotonic decrease in the plateau
modulus, (3) at high polymer concentration no peak in
the modulus is observed and (4) the modulus peak shifts
towards lower surfactant concentration as the polymer
concentration is lowered. According to Alami et al. [127]
the polymer concentration at which the onset of hydropho-
bic micro-domains arise can be influenced by the addition
of nonionic surfactants. The hydrophobic micro-domains
form at much lower concentrations than the CAC or CMC
when nonionic surfactants are present in the polymer solu-
tion. The study by Alami et al. [127] provided a schematic
presentation of the interactions between the SDS surfac-
tant and HEUR polymers in solution. Depending on the
concentration of the surfactant and the polymer, different
structures (associated polymer aggregates) are formed
(Fig. 27).
The study [127] also shows that it is difficult to dis-
tinguish a concentration region where only micelles are
formed when a HEUR polymer with a high molecular
weight is used. The formation of micelle clusters starts close
to the CMC.
At low (SDS) surfactant concentration
(csurfactant < cmcsurfactant ) the interaction of the surfac-
tant is mainly with the hydrophobic ends of the polymer
chains, which leads to a stronger network and thus an
enhanced solution viscosity [124,127,164,182,353–356].
High surfactant concentration leads to a destabilized
network as the hydrophobic end groups are solubilized,
which results in a reduction in the viscosity. In addition an
interaction between the SDS surfactant and oxyethylene
1601
of the polymer chain has been found [164,182,354–356].
In comparison, cationic surfactants only interact with the
hydrophobic end groups [127,354]. Interactions between
nonionic surfactants have been demonstrated where a
large increase in solution viscosity is observed upon addi-
tion of the surfactant [124,127,353,358,359]. The study by
Kim et al. [358] investigated the stability of the polymeric
solution employing the HEUR polymer 37(1) with the
polyoxyethylene stearyl ether (C18 [EO]20 ) surfactant in
complex formulations. An important observation made,
in the context of EOR-applications, was the stability of
the micellar network in solution in an oil-water emulsion,
despite the changes in ionic strength (different NaCl
concentrations) and pH.
In order to facilitate the investigation of molecular
weight of HEUR polymer the hydrophobic associations
have to be suppressed. Cyclodextrins, cyclic oligomers
consisting of 6, 7 or 8 glucose units (corresponding to ␣-,
␤-, ␥-CD) connected by ␣-1,4-glucosidic linkages [360],
are capable of encapsulating the hydrophobic groups
thus inhibiting hydrophobic associations. The interaction
between cyclodextrins and the HEUR polymers 37(1), 44
and 49 (2, F8 –F8 ) support this. A schematic presentation
illustrating the interactions at different stages is given in
Fig. 28.
Depending on the cyclodextrin concentration three
different regions can be distinguished [314,361,362]. At
low cyclodextrin concentration encapsulation of the end
groups of the loops occurs making the network more
susceptible to shear thinning. At moderate cyclodex-
trin concentration detachment of the bridging chains
between micelle clusters occurs, which weakens the net-
work and thus results in a lower viscosity. A further
increase in the cyclodextrin concentration leads to the
complete destruction of the network formation leaving
only individual clusters or polymer chains in solution. The
viscosity of such a polymeric solution equals the solute
viscosity.
1602 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

Fig. 28. Interactions between cyclodextrins and a HEUR polymer.

Reproduced with permission from [361] 2007, ACS Publishing.

3.3. Hydrophobically modified alkali swellable emulsion
(HASE)
HASE systems are emulsions at low pH where the
polymers exist as macroscopic particles (non-transparent
solution). As the pH is increased the particles will swell
and dissolution follows. These polymers have not been
studied as extensively as the HMPAM or HEUR polymers
[363]. However they represent an alternative to the non-
ionic HEUR polymers for applications as thickeners [363].
HASE polymers are terpolymers consisting of methacrylic
acid, ethyl acrylate and a hydrophobic group [169,364,365].

Fig. 29. Chemical structure of a HASE polymer.

 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
The HASE polymers are, as mentioned before, insoluble
in low pH solutions and require higher pH (above pH 6)
for solubilization. This, given the salinity of most reser-
voir water, is beneficial for application in EOR. In most
cases the ratio between methacrylic acid and ethyl acry-
late (i.e. molar ratio x/y) equals 1 and the hydrophobic
group is incorporated at a level of a few mol percentages
(%). The HASE polymers can be seen as polyelectrolytes,
which have been hydrophobically modified by the intro-
duction of a few mol% of a hydrophobic group. Comb-like
structure where the hydrophobic groups are placed on
short PEO side chains randomly distributed along the back-
bone of the HASE polymer chains are favored [169,363].
The backbone of the HASE polymers possesses moderate
high molecular weight and can reach 200,000–250,000 Da
[169]. The general chemical structure of a HASE polymer
[106,169,366,367] is given in Fig. 29 while a more general
overview of all studied systems can be found in Table 3.
HASE polymers are synthesized using an emul-
sion copolymerization process [181,363,372]. The three
constituents, methacrylic acid, ethyl acrylate and the
hydrophobic macromonomer, are added to the reac-
tion mixture along with an initiator. The hydrophobic
macromonomers act as the surfactant for the polymeriza-
tion reaction. These are produced by first ethoxylating a
hydrophobic group and subsequently reacting the prod-
uct of the ethoxylation with an unsaturated isocyanate
[363,364,367]. The reaction product of the emulsion poly-
merization is the HASE polymer.
Different types of hydrophobic groups have been used
which include alkyl groups [106,363,367,369,370], com-
plex poly(alkylaryl) moieties [91,363] and hydrophobic
groups containing pyrene for investigation of the associ-
ation structures [365,373–375].
The length of the PEO groups to which the hydropho-
bic groups are attached can be manipulated by controlling
the number of CH2 CH2 O moieties [169,363]. In addition the
length of the hydrophobic group can be altered by using
longer or shorter hydrophobic agents [367]. The hydropho-
bicity of the hydrophobic groups can be manipulated [169].
The number of hydrophobes per chain can be controlled
by the variation of the proportion of the macromonomer
(Fig. 29) in the recipe during the polymerization stage.
These controls offer unique possibilities for tailoring the
chemical structure, and thus the rheological properties of
the HASE polymer solutions [376].
The structure in solution is dependent on the molecular
structure of the HASE polymer. Giving the molecular struc-
ture of the polymers 51, a comb-like structure is obtained
with hydrophobic groups tethered through oxyethylene
spacers to the polymer backbone [363].
The structure of HASE polymer in aqueous solution has
been elucidated (see Fig. 30). By using superposition of
oscillations on steady shear flow [366] of HASE solutions
or in simple salt solution [369] a model was developed.
Above a given polymer concentration, the unimers will
form oligomers consisting of two or more polymer chains.
When the polymer concentration increases, the size of
the aggregates will increase. Using spin-echo (PGSE) NMR
Nagashima et al. [370] concluded that the distribution
of hydrophobes among the polymer chains is inhomoge-
1603
neous. Two distinct regions can be identified, which are
a hydrophobe enriched one and a hydrophobe depleted
one. The hydrophobe enriched region will form more
compact structures compared to the other region. By using
fluorescence studies, Prazeres et al. [374] investigated the
association level in the polymer series 54 and found that in
aqueous solution 58% of the hydrophobic pendants asso-
ciate compared to only 5% in tetrahydrofuran (THF). The
same authors demonstrated though, that the coil expan-
sion caused by the aqueous basic conditions will lead to a
large portion of the hydrophobic pendants (21 ± 6%) being
excluded from associated microdomains. This portion is
much larger when compared to polymer solutions in THF.
Varying the length of the hydrophobe groups and the
oxyethylene spacers will induce changes in the strength of
the polymer network. Increasing the hydrophobe length,
i.e. the hydrophobicity, will lead to stronger associations
and thus a stronger network. This behavior was demon-
strated by Tirtaatmadja et al. [367] which is in line with
findings using polyacrylamides and poly(ethylene oxide).
Increasing the length of the oxyethylene spacers increases
the accessibility of the hydrophobes, which in turn leads to
easier formation of hydrophobic domains [169] and there-
fore a stronger network. However, if the length exceeds
a certain critical length intramolecular associations are
favored causing a collapse of the network [169].
3.3.1. Rheological properties
The rheological properties of HASE polymers in aqueous
solution are dependent on the solubilization conditions.
When using alkali media, the backbone of the HASE
polymer chain becomes hydrophilic and will dissolve in
aqueous solutions. The hydrophobic groups of the HASE
polymer will form associations, either intra- or interchain
interactions, which will cause a significant increase in the
solution viscosity [369].
The dissolution of HASE polymers has been investigated
by several authors [167,168,377]. The data obtained using
potentiometric titration, isothermal titration calorimetry
and dynamic light scattering studies, led to the elucidation
of the dissolution mechanism of the HASE polymers, either
in the presence or absence of salt (Fig. 31).
The size (hydrodynamic radius, Rh ) of the latex par-
ticles increase in size as the pH rises (increase in base
concentration) due to the electrostatic repulsions. For a
HASE polymer latex particle in a salt solution the size
increases but to a lesser extent due to shielding of the neg-
ative charges on the polymer backbone by the cations, i.e.
Rh, no salt > Rh, salt
The electrostatic repulsion forces between the chains
also alter the configuration of the polymer aggregates. The
thickening capability of the HASE polymers is a combina-
tion of hydrophobic association and the expansion of the
polymer chains [181,370]. At low polymer concentration,
the intramolecular hydrophobic interactions dominate
while at higher polymer concentration the situation arises
where predominantly intermolecular hydrophobic inter-
actions are present [370]. The intermolecular hydrophobic
interactions give rise to network formation thus enhanc-
ing the viscosity of the polymer solution [366,367,370].
Knaebel et al. [378] provided a schematic presentation
 1604
Table 3
Structure of different water-soluble polymers, HASE.

Polymer Structure References

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

Polymer based on methacrylic acid (MAA), ethyl acrylate (EA) and a hydrophobic [169]
macromonomer (associative macromonomer, AM).

R = H (1), C8 H17 (2), C12 H25 (3), C16 H33 (4) or C20 H41 (5)
m = 33 (for 2)
m = 35 (for 1, 3–5)
X–Y–Z (1) = 48.76–51.24–0.00 (mol%)
X–Y–Z (2) = 49.00–50.00–1.00 (mol%)
X–Y–Z (3) = 49.05–50.05–0.90 (mol%)
X–Y–Z (4) = 49.06–50.04–0.90 (mol%)
X–Y–Z (5) = 49.06–50.04–0.90 (mol%)

Polymer based on methacrylic acid (MAA), ethyl acrylate (EA) and a hydrophobic [106,169,366,367]
macromonomer (associative macromonomer, AM).

Serie A, N = 19 and m = 0, 10, 15, 35 or 40

Serie B, m = 35 and N = 4, 8, 12, 16 or 20
X–Y–Z (A&B) = 49.06–50.01–0.90 (mol%)
Table 3 (Continued)

Polymer Structure References

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

Polymer based on methacrylic acid (MAA), ethyl acrylate (EA) and a hydrophobic [363,366–368]
macromonomer (associative macromonomer, AM).

m = 80
X–Y–Z = 40.00–40.00–20.00 (wt.%)

1605
 1606
D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
Polymer based on methacrylic acid (MAA), ethyl acrylate (EA) and a hydrophobic [91,371]
macromonomer (associative macromonomer, AM).

m = 53
X–Y–Z (Refs. [169,369,370]) = 45.00–55.00–<1.00 (mol%)
X–Y–Z (HASE65) = 0.49–0.49–0.021
X–Y–Z (HASE48) = 0.50–0.49–0.011
X–Y–Z (HASE42) = 0.44–0.55–0.011
X–Y–Z (HASE35) = 0.45–0.55–0.006
X–Y–Z (HASE12) = 0.40–0.59–0.002
X–Y–Z (HASE11) = 0.40–0.69–0.0035
X–Y–Z (HASE0) = 0.40–0.59–0.002
 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628 1607

Fig. 30. Microstructure as proposed by Dai et al. [369].

Reproduced with permission from [369] 2000, ACS Publishing.

illustrating the structural transitions that a HASE polymer
undergoes when the polymer concentration is increased,
from low to a high concentration, in an alkaline polymer
solution (Fig. 32).
A schematic presentation of the microstructure of the
polymer chains at very low polymer concentration in an
alkaline solution, as proposed by Dai et al. [369], is given in
Fig. 32. At low polymer concentration a colloidal suspen-
sion is present, i.e. no solubilization of the polymer chains.
The microstructure of the polymer chains at low polymer
concentration consist of a unimer with the hydropho-
bic domain in the center and the hydrophilic backbone
extended in the solution. As the polymer concentration
is increased a transition to an overlap regime occurs. This
transition takes place above the cross-over concentration
(Cg ) [378] and leads to a significant rise in the viscosity of
the HASE polymer solution due to the interactions between
the hydrophobic groups. The structure of the network has
been investigated and a schematic presentation has been
provided by Tan et al. [379] (Fig. 33).

Fig. 31. Dissolution mechanism in the absence and presence of salt.

Reproduced with permission from [168] 2002, ACS Publishing.

Fig. 32. Concentration regimes for HASE polymers in an alkaline solution.

Reproduced with permission from [378] 2002, John Wiley and Sons.
1608 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
There are a number of different interactions in
the network of HASE polymers, which are the intra-
and intermolecular hydrophobic interactions, polymer
chain entanglements and electrostatic interactions. Araujo
et al. [180] demonstrated the presence of two different
hydrophobic micro-domains using various pyrene deriva-
tives as probes. The ethyl acrylate rich micro-domains
(Fig. 33) are what Araujo et al. [180] envisaged.
Most HASE polymer solutions exhibit a strong pseu-
doplastic behavior when sheared, which is preceded by a
weak shear thickening region [106,378]. The latter arises
due to the disruption of the hydrophobic intermolecu-
lar associations by shear [365]. Thixotropic behavior was
also noticed by Knaebel et al. [378], similar to polymeric
solutions containing HMPAM. Increasing the polymer con-
centration leads to an increase in the zero-shear viscosity.
However, the shear rate at the onset of shear thinning
shifts to lower values when the polymer concentration is
increased [378].
3.3.2. Effect of inherent parameters
The effects of length of the PEO spacers, hydrophobic-
ity of the hydrophobic group, length of the hydrophobic
groups and the molecular weight of the HASE polymer
on the rheological properties of HASE polymer solution
have been elucidated. As discussed earlier, when the
length of the PEO spacers is increased the accessibility
of the hydrophobic groups for hydrophobic associations
increases. This leads to a lower number of larger hydropho-
bic micro-domains. However if the length of the PEO
spacers surpasses a critical length intramolecular associa-
tions will be the dominant type of hydrophobic interaction
[169]. The strength of the polymer network reduces and
a decrease in the solution viscosity follows. This was
observed by Tam et al. [380] who demonstrated that
PEO spacers with a moderate length displayed the high-
est steady shear and zero shear solution viscosity. The
more pronounced shear thinning and viscoelastic behav-
ior arose with the same polymer. Changing the type of
hydrophobic groups, i.e. its hydrophobicity or length, also
affects the polymer network and thus its rheological prop-
erties. Increasing the hydrophobicity or the length of
the hydrophobic groups will increase the strength of the
hydrophobic associations [169,367,376]. This translates
Fig. 33. Network structure of a HASE polymer.
Reproduced with permission from [379] 2001, John Wiley and Sons.
into a higher steady shear and zero shear solution viscos-
ity but also to a more pronounced pseudoplastic behavior.
Using the polymer series 51 the positive effect of the
length or size of the hydrophobe on the solution viscosity
was demonstrated [367,376]. The highest solution viscosity
was obtained with the longest/largest hydrophobic group
(C20 ). Using polymer 52 English et al. [371] demonstrated
that by using more complex hydrophobic groups the net-
work dynamics of the polymer is no longer represented
by a single characteristic relaxation time but by rather
the hindered reptation model put forward by Leibler et al.
[291]. The deviation of the classical Maxwellian behav-
ior arises by the coexistence of hydrophobic associations
and chain entanglements [371]. Ng et al. [381] investi-
gated the difference in solution viscosity in HASE polymers
compared to the unmodified analogue. Fig. 34 schemat-
ically represents the differences hypothesized by the
authors.
The hydrophobic groups will interact with the ethyl
acrylate blocks in the semi-dilute concentration regime.
These in turn will enhance the intermolecular associations
between different clusters. The higher solution viscosity of
the hydrophobically modified polymers compared to the
unmodified analogues is attributed to this enhancement.
As mentioned before the hydrophobicity of the hydropho-
bic groups will affect the rheological properties of the HASE
polymer. A classic example of this is the polymer series 54
[365]. The polymer with the pyrene functionality displayed
a higher solution viscosity compared to the same polymer
without pyrene. However, the number of intermolecular
hydrophobic associations that arise is dependent on the
pyrene content with more being formed at lower pyrene
contents.
The degree of ethoxylation affects the thickening capa-
bility of HASE polymers. The optimum ethoxylation degree
lies between 5-40 mol% of the ethylenoxide on the
hydrophobic monomer [380]. According to Wu and Shay
[376], the balance between hydrophobic associations and
electrostatic repulsion can be manipulated by the incor-
poration level of the methacrylic acid moiety [376]. The
maximum zero shear rate viscosity is obtained with an
incorporation rate of 40 wt%. A classic example of this
behavior is observed for polymer 51. In addition it was
demonstrated that the optimum ethoxylation degree cor-
 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
Fig. 34. Schematic presentation of the associations in HASE and its unmodified analogue.
responds to the dominant elastic property of the polymer
system at 10 mol% ethyleneoxide [380].
Another factor that affects the rheological properties is
the molecular weight and this can be controlled by the
amount of chain transfer agent (CTA) used during the emul-
sion polymerization. Increase in molecular weight results
in higher zero shear and steady shear solution viscosity
[376], unlike HEUR polymers where the exact opposite
behavior is observed. In addition the authors observed that
a reduction in molecular weight leads to a system where
the Newtonian plateau is more extended.
3.3.3. Effect of external parameters
The effect of pH and ionic strength on the rheology of
the HASE polymer solutions has also been investigated.
At relatively low pH, the HASE polymers are insoluble
given the uncharged nature of the carboxylic acid groups
[181]. Due the presence of methylacrylic acid in the back-
bone of the HASE polymer alkaline pH will ionize these
groups and will lead to swelling of the polymer and the
formation of a polyelectrolyte with solubility in water
[169,181,367,368,370]. The swelling of the polymer is a
result of the electrostatic repulsion between the poly-
electrolyte chains [169,368,379]. As the pH is increased a
smaller number of larger hydrophobic micro-domains are
formed, which leads to an increase in the solution viscos-
ity [181]. The expansion of the polymer chain is partly
a result of the dissolution of the particle (present prior
to the solubilization) [181]. In order to investigate the
association mechanisms of HASE polymers the hydropho-
bic micro-domains of polymer 51 (5) were probed using
Fig. 35. Model illustrating the network structures of HASE in salt under shear.
Reproduced with permission from [379] 2001, John Wiley and Sons.
1609
pyrene [181]. At a pH of 5.7 a large number of hydropho-
bic micro-domains are present. As the pH of the polymer
solution is raised a smaller number of larger hydropho-
bic domains are formed. The authors suggest a transition
from intramolecular to intermolecular hydrophobic asso-
ciations. This leads to a significant increase in the solution
viscosity.
Adding salt to the polymer solution affected its rheolog-
ical properties. Increase in the salt concentration resulted
in a decrease of the solution viscosity with the effect being
more pronounced for groups with higher hydrophobicity.
However, the polymer 51 (with C20 H41 as the hydrophobe)
displayed a shear thickening behavior at a given salt con-
centration [368]. The first effect, significant reduction in
the solution viscosity [379] with the addition of salt, is
attributed to the shielding of the charges on the polymer
backbone leading to the shrinkage of the polymer back-
bone. The intermolecular hydrophobic associations will be
destroyed due to the shrinkage. The second effect, shear
thickening with the addition of more salt, is attributed to
the reformation of the network. The authors [379] have
provided a model illustrating the network structures in salt
solution under shear deformation (Fig. 35).
Several different studies [91,106,375,382–384] have
been published on the interactions between HASE poly-
mers and different surfactants. Polymers 51 (5) and 53 have
been shown to interact with surfactants. Depending on
the nature of the surfactant different behaviors can arise
[91]. Using a partially water-soluble nonionic surfactant
(nonylphenol ethoxylate) English et al. [91] demon-
strated that the shear rate range where shear induced
1610 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
Fig. 36. Interactions between nonionic surfactant and HASE polymers.
Reproduced with permission from [384] 1998, John Wiley and Sons.
structuring of the polymer network occurs can be widened.
The use of water-soluble nonionic surfactant, at high suffi-
cient surfactant concentration, resulted in the loss of shear
induced structuring of the polymer network. It was further
demonstrated that, when using water-soluble surfactants,
segregation occurs where two distinct systems exists, one
phase rich in polymer and one rich in surfactant. On the
contrary, by using a partially soluble surfactant no evi-
dence of complete segregation was found. A few studies
[382–384]demonstrated the increase in viscosity of the
polymeric solution, employing polymer 51 (5), when using
nonionic surfactant (C12 EO4 ). The increase in the viscos-
ity was noticed up to a surfactant concentration of 0.1 M.
The studies attributed the increase in solution viscosity
to the formation of mixed micelles of surfactant and the
hydrophobic groups of the HASE polymer chains. At sur-
factant concentrations above 0.01 M stronger interactions
arise, thus a strengthening of the polymer network, where
the formation of a stiff gel-like structure occurs. At this
stage a bilayer is formed by the surfactant molecules, which
are stabilized as large vesicles. A schematic presentation, as
provided by Tirtaatmadja et al. [384], of the interactions
between the nonionic surfactant, at different surfactant
concentration, and the HASE polymer is given in Fig. 36.
The temperature affects the interactions between the
surfactant and HASE polymers. At low to moderate (non-
ionic) surfactant concentration the solution shear viscosity
decreases with increasing temperature. Above a certain
shear rate a substantial decrease in viscosity is observed,
which can be related to the characteristic relaxation time
associated with the dissociation of hydrophobes from
hydrophobic domains. The rate of dissociation is much
higher than the rate of association [385]. However this con-
cept, i.e. the relation between characteristic relaxation time
and exit rate of hydrophobic groups, as proposed by Aubry
and Moan is controversial and needs verification [383]. Tam
et al. [106] investigated the interactions between polymer
51 (5) and the nonionic surfactant (C12 EO23 ). The addition
of the nonionic surfactant resulted in the strengthening
of the polymer network by the increase of the number of
intermolecular hydrophobic associations similar to when
C12 EO4 was used as the nonionic surfactant. According to
the study [106] the polymer-surfactant interactions are
entropically driven.
Interactions between ionic surfactants and HASE poly-
mers have also been demonstrated [373,382]. The positive
effect, i.e. increase in solution viscosity, of the surfactant
on the rheological property arises due to the same effect as
with nonionic surfactant. Seng et al. [382] investigated the
interactions between polymer 51 (5) and the SDS surfac-
tant. Above a given critical surfactant concentration (CS*),
closed to the CMC of the surfactant, the aforementioned
positive effect is lost due to the disruption of the poly-
mer network [382]. This leads to a reduction in the number
of hydrophobic micro-domains. In addition free cations of
the surfactant molecules screen the anionic charges on the
HASE polymer backbone, which reduces the electrostatic
repulsion between chains. A model representing the dif-
ferent molecular interactions between a ionic surfactant
and polymer 51 (5) has been provided by Seng et al. [382]
(Fig. 37).
The interactions of SDS with polymer 51 (5) can be
divided into three regions (1, 2 and 3 in Fig. 37). In regions
1 and 2 the effects of the polymer–surfactant interactions
on the rheology are limited. However, in region 3 weaken-
ing and destruction of the polymer network arise due to on
one hand shielding of the charges (less electrostatic repul-
sion and thus decrease in hydrodynamic volume) and on
the other hand the isolation of the hydrophobes in micelles
thus suppressing intermolecular hydrophobic associations.
Both of these effects lead to a lower solution viscosity.
The same interaction behavior is observed with SDS and
polymer 53 [373]. This in marked contrast to the behav-
ior of nonionic surfactants discussed earlier. Nevertheless
the same behavior, loss in solution viscosity at high surfac-
tant concentration, has also been reported for a nonionic
surfactant (polyoxyethylene) [106].
3.4. Hydrophobically modified cellulose derivatives
The current demand for environmental-friendly
materials is relevant also for EOR applications. Hydropho-
bically modified hydroxyethyl cellulose (HM-HEC),
hydrophobically–hydrophilically modified hydroxyethyl
cellulose (HHM-HEC), hydrophobically modified hydrox-
ypropyl cellulose (HM-HPC) or hydrophobically modified
ethyl hydroxyethyl cellulose (HM-EHEC) polymers can
meet these demands. The parent cellulose polymer is a
nonionic polysaccharide, which possesses anti-bacterial
properties [386]. Parent cellulose polymers are hydropho-
bically or/and hydrophilically modified to produce the
HM-HEC, HHM-HEC, HM-EHEC or HM-HPC polymers. A
general structure of hydrophobically modified cellulosic
polymer is presented in Fig. 38.
 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
Fig. 37. Molecular interactions between SDS and polymer 43 (5).
A general overview of the reported systems is given in
Table 4.
A synthesis method, described by Miyajima et al. [406],
for HM-HEC polymers involves a one-pot synthesis. A reac-
tor is charged with the HEC polymer and isopropyl alcohol
together with an aqueous solution (48%) of sodium hydrox-
ide. This slurry is stirred at room temperature for 30 min
under a nitrogen atmosphere after which the hydrophobic
reagent is introduced. The reaction is then performed for
several hours (e.g. 8 h) at 80 ◦ C. Methods for the synthe-
sis of different HM-EHEC polymers have been developed
and provided by Boström et al. [407] and Landoll [98].
These comprise several steps. First the cellulose is isolated
from wood pulp using standard techniques, i.e. using a
21.5 wt% aqueous sodium hydroxide solution for 30 min.
Then hydroxyethyl groups are introduced by reaction with
ethylene oxide at 50 ◦ C for 75 min. The last step involves
the incorporation of the hydrophobic group by reaction at
105 ◦ C for 120 min.
The presence of hydrophobic groups on the polymer
backbone of the polysaccharides will cause the formation
of associations just like the HMPAM, HEUR and HASE ana-
logues. The network structure is enhanced due to these
groups and the hydrophobic associations arise at very low
polymer concentration [118,399,405,407–409]. Polymers
56, 57, 58, 61 and 63 are classic examples of this behav-
ior with associations commencing at very low polymer
concentrations. When good solvents are used, e.g. alco-
hols or dioxane, no associations arise [118]. Polymers 56,
57, 58 and 63 impart a stronger network when compared
to their unmodified analogues. The type of hydrophobic
Fig. 38. General chemical structure of hydrophobically modified cellu-
losic polymer.
1611
group also affects the strength of the network. Increas-
ing the hydrophobicity will increase the strength. Polymer
57 and 60 (R1 = 2) are examples where the polymer with
fluorocarbon provide a stronger network than the hydro-
carbon (un)modified analogue [391]. The distribution of the
hydrophobic groups is also of crucial importance. Polymer
62 represents an example in which, due to inhomoge-
neous distribution of the hydrophobic group, two separate
phases of polymers are observed [401]. One containing
highly substituted chains and another with less substitu-
tion. The highly substituted chains will be preferentially
incorporated into the network.
Classical polyelectrolyte behavior can be obtained by
the incorporation of charged moieties in the backbone
of the polysaccharides. An example of this behavior is
observed with polymer 60 (R1 = 3) where cationic moieties
are incorporated into the backbone of the polysaccharide
[397].
3.4.1. Rheological properties
Although different types of hydrophobically modified
polysaccharides have been synthesized their rheological
properties in aqueous solution depend on the modifi-
cation rather than on the type of polysaccharide used.
The hydrophobic modifications introduced on the differ-
ent cellulose derivatives decrease the solubility of the
polysaccharide. Several studies have demonstrated the
pseudoplasticity of hydrophobically modified polysaccha-
rides. Typical shear thinning is observed similar to the
hydrophobically modified polyacrylamides. However, the
concentration of the polymeric solution has to be high
enough before pseudoplastic behavior is observed. Polymer
59 is a classic example of this behavior [395]. In addi-
tion shear thickening behavior is observed. The presence
of shear thickening only arises within a certain concentra-
tion range of approximately 0.15–0.5 wt%. The zero-shear
solution viscosity of a polymer solution is much more
dependent on the concentration in the lower concentra-
tion regime. Increasing the polymer concentration also
decreases the dependency of the zero-shear viscosity on
concentration [410]. Examples of the shear thickening
 1612
Table 4
Structure of different water-soluble polymers, HMHEC.

Polymer Structure References

HHM-HEC

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

The hydrophobic groups are long alkyl chains and the hydrophilic groups are sodium sulfonate [106]
groups.

HHM-HEC, R2 = –n–C18 H37 and R3 = 1

S-HEC, R2 = H and R3 = 1
R-HEC, R2 = –n–C18 H37 and R3 = H

HM-HEC

Commercial product, produced by different suppliers. [386]

Table 4 (Continued)

Polymer Structure References

HM-HEC

The hydrophobic groups are fluorocarbon chains [386–389]

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

HM-HEC

EP16-HAHEC, R2 = 1 [390]

IPBC-HAHEC, R2 = 2
BD-HAHEC, R2 = 3

HM-HEC

Hydrophobic groups are alkyl chains varying between 8 and 40 carbons in length [391]

1613
 1614
HM-HEC

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

R3 , R4 and R5 = alkyl, aryl, aralkyl, alkaryl, cycloalkyl, alkoxyalkyl and alkoxyaryl where a [392–394]
maximum length of 10 C-atoms (the total length of R3 , R4 and R5 is between 3 and 12 C-atoms.
When R3 , R4 or R5 is an alkoxyalkyl radical two C-atoms separate the O and N-atom.

The N-atom is a component of: pyridine, ␣-methylpyridine, 2,5-dimethylpyridine,

2,4,6-trimethylpyridine, N-methylpiperidine, N-ethyl piperdine, N-methyl morpholine or
N-ethyl morpholine.
R1 = 2, flourocarbon groups
R1 = 3, cationic groups
R1 = 3 and 4, cationic and hydrophobic groups randomly distributed
R1 = 5, cationic hydrophobic groups
Table 4 (Continued)

Polymer Structure References

HM-HPC

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

The polysaccharide is labeled with pyrene (1) or fluorene (2) groups for fluorescence studies [395,396]

HM-EHEC

The hydrophobic groups are either long alkyl chains or a nonylphenol group [397–399]

1615
 1616
HM-HEC-py-1

The hydrophobic groups are an alkyl chain and a pyrene group for fluorescence studies [118,400]

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

HM-CMC

The hydrophobic groups are amino-terminated poly(N-isopropylacrylamide) [307,401–404]

HM-Alginate

The hydrophobic groups are n-octylamines [405]

 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
behavior are polymers 55 [386,387] and 59 [410,411] and
an example of a polymer which does not display shear
thickening due to a high concentration is polymer 58
[392–394].
Thixotropic behavior is also observed for the hydropho-
bically modified polysaccharides. Similar to other
hydrophobically modified polymers, such as HMPAM,
hysteresis effects can be seen for polymeric solution
employing polymer 55 (HHM-HEC, R-HEC) [387], 56 [412],
58 [392–394], 59 (hydrophobic groups are hexadecyl
moieties) and 60 (R1 = 2, R1 = 5) [397,399]. The viscosity
of the polymeric solution at increasing shear rates is
higher compared to the viscosity of the same solution
when the shear rates decrease. According to Maestro
et al. [413] hydrophobically modified polysaccharides dis-
play thixotropic behavior due to the diffusion controlled
migration of hydrophobes to micelles.
3.4.2. Effect of inherent parameters
The presence of hydrophobic groups leads to an increase
in the solution viscosity of HM-polysaccharides. Similar
to other hydrophobically modified polymers associations
between the hydrophobic groups arise which lead to a
strong polymer network. The behavior, significant increase
in the zero-shear viscosity, was noticed for solutions
employing either polymer 58 [392–394] or polymer 64
[405].
As mentioned before, the incorporation of charged
moieties affects the network structure of HHM-
polysaccharides. Therefore the rheological properties
are also affected. In principle the thickening capability
of the charged polysaccharide is higher compared to the
uncharged analogue [386]. The HHM-HEC polymer 55 is an
example of such a charged polysaccharide where sulfonic
groups are incorporated into the backbone.
3.4.3. Effect of external parameters
In principle the presence of salt does not affect the
rheological properties of HM-polysaccharides solutions.
However, it has been demonstrated that the presence of
salt leads to a stronger hydrophobic network and thus an
increase in the solution viscosity. Polymer 57 is an example
of this behavior [391]. When charged moieties are incorpo-
rated into the backbone of the HM-polysaccharides, screen-
ing of the electrostatic repulsion arises in the presence of
electrolyte. In classic polyelectrolytes, this screening leads
to a collapse of the polymer coils and a significant reduction
in the solution viscosity. However, for the polysaccha-
rides modified with hydrophobic groups (in addition to
the charged groups), this behavior is not observed. Indeed,
the presence of salt will weaken the electrostatic repulsion.
However this leads to the enhancement of the hydropho-
bic associations and thus a strengthening of the polymer
network. In addition to the presence of salt, the type of
salt is also important for the observed behavior. According
to Picton and Muller [412], the presence of salts that are
able to induce a structuring of the water molecules, will
lead to an enhancement of the viscosity due to the increase
number of hydrophobic association. However using other
types of salts, e.g. potassium thiocyanate, the enhancement
1617
in solution viscosity is not as pronounced [412]. Solutions
containing polymer 56 display this behavior.
The ratio between the hydrophobic/hydrophilic sub-
stitution significantly affects the solution properties at
low polymer concentration [389]. The thickening capa-
bility is increased when this ratio is high. Polymer 55
is an example of a polymer whose thickening capability
increases with a high hydrophobic/hydrophilic substitu-
tion [387,388]. Fig. 39 displays the effect of the presence
of salt on the polymer network that has been envisaged by
Kawakami et al. [387].
As the concentration of the salt increases, the electro-
static repulsion is reduced. This leads to a reinforcement
of the hydrophobic associations and thus a stronger poly-
mer network. Akiyama et al. [389] agree up to a point with
the model presented in Fig. 39. However, an expansion
is introduced in that the salt effect is also dependent on
the hydrophobic/hydrophilic ratio. When the hydropho-
bic microdomains of the polymer network are saturated,
i.e. when there are no free hydrophobes for association,
the effect (reinforcement of the hydrophobic association)
depicted in the model will not occur. The addition of salt
will lead to a reduction of the electrostatic repulsion but
the hydrophobic associations will not be reinforced given
their strength prior to the addition of the salt. On the other
hand if the hydrophobic microdomains are not saturated,
i.e. when there are free hydrophobes, than the model pre-
sented in Fig. 39 can be held valid.
The solution hysteresis (as a function of the shear rate)
is affected by the presence of salt. Increasing the salt con-
centration will suppress the tendency of the solution to
display hysteresis, and increasing the salt concentration
beyond a certain limit no hysteresis behavior is observed.
An example of such a solution is the solution with polymer
55 (R-HEC) [387].
The temperature affects the viscosity of hydrophobi-
cally modified polysaccharides. In most cases the viscosity
is reduced as the temperature is increased. This behav-
ior has been observed with polymer 55 and 62 (R = 1)
[402]. In addition, the aggregation of hydrophobes is also
affected by temperature. By using polymer 61, Winnik
[414] demonstrated that upon increasing the temperature
the hydrophobic associations are less stable, which leads
to a weaker polymer network. The dependence of the vis-
cosity on temperature was also observed with polymer 56
[415]. The shear thickening and shear thinning remained
the same but the viscosity values changed as a function of
temperature.
Similar to HMPAM, HEUR and HASE polymers
hydrophobically modified polysaccharides also dis-
play interactions with different types surfactants, i.e.
anionic, cations or nonionic. The surfactants that have
been demonstrated to interact with hydrophobically
modified polysaccharides are listed in Table 5.
The interaction between HM-HEC and a surfactant leads
to different behaviors depending on the concentration of
the surfactant and the type of surfactant. When using the
anionic surfactant SDS, the surfactant molecule will inter-
act with the hydrophobic groups forming mixed micelles.
The formation of these mixed micelles will increase
the number of hydrophobic microdomains and will
1618 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628

Fig. 39. Schematic model of the effects of added salts.

Reproduced with permission from [387] 2006, ACS Publishing.

enhance interpolymer associations and thus strengthen
the polymer network [307,415,420,423]. Increasing the
surfactant concentration further will lead to electrostatic
repulsions between the mixed micelles and subse-
quently a drop in the solution viscosity of the ternary
(water–polymer–surfactant) system [423]. The viscosity
of the polymeric solution employing polymer 55, 57,
62 (R=1) or 65 increases and passes through a maxi-
mum as the concentration of the anionic SDS surfactant
is increased [408,416,432]. The reduction in solution
viscosity at elevated surfactant concentration can be
counteracted by increasing the surfactant aggregation
number in the mixed micelles. This can be achieved by
either adding screening electrolytes or oppositely charged
surfactants [433]. A polymer–surfactant solution employ-
ing a surfactant with a lower CMC will reach a maximum
solution viscosity at lower surfactant concentration com-
pared to a surfactant with a higher CMC [430].
The zero-shear viscosity of a polymer solution passes
through a maximum with the addition of a nonionic
surfactant (Cm EOn ), similar to the behavior with an
anionic surfactant [415]. Increasing the temperature of
the polymer–surfactant solution leads at first to a reduc-
tion in the solution viscosity. However, beyond this region
a considerable increase in the viscosity is observed until
the cloud point temperature of the solution is reached.
This increase in solution viscosity is attributed to the
interchain association caused by micellar aggregation
[415].
The surfactant binding mechanism to the hydrophobes
of HM-EHEC depends on the surfactant concentration. It
was demonstrated that at low surfactant concentration
the hydrophobic microdomains act as nucleation sites
onto which the surfactants preferentially absorb [426,428].
An increase in the surfactant concentration leads to a
transition from non-cooperative binding to a more cooper-
ative binding [417,426] similar to the unmodified analogue
(EHEC) in polymer–surfactant solution [426]. In addi-
tion, the data indicate that the number of hydrophobic
microdomains is constant with respect to the surfac-
tant concentration. According to Evertsson and Nilsson
[417], the strongest interaction, in terms of the highest
microviscosity, is achieved when the surfactant binds in
non-cooperative way at very low adsorption degree of SDS.
The polymer concentration also has an effect on the type
of interaction that is observed between surfactants and
HM-EHEC. With the addition of surfactant (SDS) to the
polymeric solution employing polymer 62 (R = 1), Lauten
and Nyström [419] demonstrated that the association com-
plexes between the polymer and surfactant will grow with
time. These complexes will eventually sedimentate due
to their size. This effect is observed at low SDS concen-
tration at both high and low polymer concentration. At
high SDS concentration the intermolecular associations are
dissolved and no time dependence is observed for the
system [419]. By using cloud point experiments, Thures-
son et al. [425] demonstrated that the solubility of the

Table 5
The different surfactants shown to interact with hydrophobically modified polysaccharides.

Surfactant Abbreviation Type Source

Sodium dodecyl sulfate SDS (NaC12 S) Anionic [117,307,408,416–428]

Sodium decyl sulfate NaC10 S Anionic [117]
Sodium tetradecyl sulfate NaC14 S Anionic [424]
Sodium dodecyl-di(ethyleneoxide)-sulfate (NaC12 [EO]2 S) Anionic [424]
Sodium alkanoate CH3 [CH2 ]n COONa, n = 4, 6, 8 and 10 Anionic [427]
Sodium octyl benzene sulfonate SOBS Anionic [427,429]
Cetyltrimethylammonium bromide CTAB Cationic [430]
Tetradecyltrimethyl ammonium bromide TTAB Cationic [420,430]
Dodecylammonium chloride C12 ACl Cationic [424]
Dodecyltrimethylammonium chloride C12 TACl Cationic [424]
Dodecyltrimethylammonium bromide C12 TABr Cationic [424]
Hexadecyltrimethylammonium bromide C16 TABr Cationic [424]
Hexadecyltrimethylammonium acetate C16 TAAc Cationic [424]
Alkyl betainate CH3 [CH2 ]n COOCH2 N[CH3 ]3 , n = 9, 11, 13 Cationic [431]
Octylphenol adduct C8 H17 C6 H4 O[EO]10 H (Triton X-100) Nonionic [418]
Polyoxyethylene alkyl-ether Cm Hn , m = 11, 12 and 13/n = 4 Nonionic [117,415,420]
 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
hydrophobically modified polymer is suppressed at low
SDS concentrations compared to its unmodified analogue.
HM-EHEC also interacts with different surfactant in a
different manner. The addition of ionic surfactants leads in
most cases to an enhancement of the hydrophobic asso-
ciations at moderate surfactant concentration. Increasing
the surfactant concentration further leads to the disrup-
tion of the hydrophobic micro-domains and thus of the
polymer network. According to Kjonikson et al. [434] the
polymer–surfactant system transits from a heterogeneous
system at low surfactant concentration to a homogeneous
one at high surfactant concentration. The interactions of
nonionic surfactants with HM-EHEC, i.e. polymer 62 (R = 1),
are weaker when compared to ionic surfactants [427]. Nev-
ertheless, for both ionic and nonionic surfactants the length
of the surfactant chain is crucial for the solution behavior.
If this length is increased the disruption of the network, i.e.
loss of solution viscosity, is postponed due to an increase
in the aggregation number of the mixed micelles [427].
One striking behavior is the influence of a spacer (EO-
spacer) between the hydrophobic group and the polymer
backbone on the solution viscosity [434] in the presence of
surfactants. At high surfactant concentrations, the behav-
ior of the polymer with or without the spacer is similar to
its unmodified non-hydrophobic analogue. The viscosity of
the polymeric solution employing the HM-EHEC with spac-
ers of 4 EO units with no surfactant is much lower compared
to the one without spacers. However, the authors [434]
correctly mention the positive effect a spacer should have
on the viscosity given the studies of Hwang and Hogen-
Esch [241] and Tam et al. [380]. Therefore the authors [434]
attribute the discrepancy to the difference in distribution
of the hydrophobes along the polymer backbone.
The presence of salt does not affect the rheological prop-
erties of a solution containing a HM-polysaccharide and a
surfactant. At intermediate salt concentration no change
in the solution viscosity is observed. However a further
increase in the salt concentration leads to a solution vis-
cosity which is higher than for a solution without the
surfactant.
4. Conclusion
This review clearly indicates that the successful design
of new water-soluble polymers for a given applica-
tion requires an integral multiscale and multidisciplinary
approach. Proper definition of the required product proper-
ties is in this case crucial. Knowledge of polymer chemical
architecture (and thus of the synthetic methods used) must
be conceptually linked to the desired product application
requirements. In this case viscosity measurements under
different shear conditions are of paramount importance
and should be ideally correlated with the “nature” (i.e. poly-
mer architecture and overall chemical composition) of the
corresponding water solution.
The influence of external parameters (e.g. pH and tem-
perature) on the rheological behavior must be coupled
with an in depth knowledge of the relationship between
the chemical structure and architecture of the polymer
and the rheological behavior. In this respect, an overall
correlation cannot be defined only as a function of the
1619
chemical/molecular structure. Rheological properties will
be affected by a combination of external parameters and
the chemical nature and molecular structure of the poly-
mer. For instance, the rheological properties of an aqueous
solution of an amphiphilic polyelectrolyte are similar to
those of an unmodified analogue without amphiphilic
moieties. However, in the presence of salt a markedly dif-
ferent behavior is observed. The solution viscosity of the
unmodified polymer decreases with increasing salt con-
centration, whereas the solution viscosity of the aqueous
solution containing the amphiphilic polyelectrolyte is not
affected. Another good example is the thermal perfor-
mance of amphiphilic polymers: the rheological properties
of an aqueous solution containing the amphiphilic poly-
mer or its unmodified analogue, i.e. without the NIPAM
monomer, are quite similar. However, when exposing both
solutions to higher temperatures significant differences
arise. The effect of temperature on the solution viscosity of
an aqueous solution containing the amphiphilic polymer is
limited, whereas the viscosity of the unmodified analogue
changes significantly.
Although there are many different water-soluble
polymers capable of enhancing the solution viscosity,
it is important to understand their differences and
analogies. Different polymers display in general differ-
ences in the agglomeration principles governing their
water behavior. On a molecular level the basic princi-
ple is indeed quite general: the presence of relatively
weak inter(macro)molecular interactions (e.g. hydropho-
bic association and hydrogen bonding) factually increases
the molecular weight of the polymer coils. As a con-
sequence the solution viscosity increases. However, a
careful balance must be observed here since predomi-
nantly weak interactions (both in terms of strength and
number thereof) do not result in observable rheological dif-
ferences while excessively strong ones might compromise
the solubility of the system by leading for example to gel
formation.
Acknowledgement
This work is part of the Research Programme of the
Dutch Polymer Institute DPI, Eindhoven, the Netherlands.
References
[1] Thomas S. Enhanced oil recovery—an overview. Oil Gas Sci Technol
2008;63:9–19.
[2] Han D-K, Yang C-Z, Zhang Z-Q, Lou Z-H, Chang Y-I. Recent
development of enhanced oil recovery in China. J Pet Sci Eng
1999;22:181–8.
[3] Li G, Zhai L, Xu G, Shen Q, Mao H. Current tertiary oil recovery in
China. J Disper Sci Technol 2000;21:367–408.
[4] Lake LW. Enhanced oil recovery. Englewood Cliffs, NJ: Prentice-Hall
Inc.; 1989.
[5] Sorbie KS. Polymer-improved oil recovery. Boca Raton, FL: CRC
Press; 1991.
[6] Levitt DB, Pope GA. Selection and screening of polymers for
enhanced-oil recovery. In: SPE Improved Oil Recovery Symp. 2008.
p. 1–18, 113845.
[7] Gaillard N, Giovannetti B, Favero C. Improved oil recovery using
thermally and chemically protected compositions based on co- and
ter-polymers containing acrylamide. In: SPE Improved Oil Recovery
Symp. 2010. p. 1–11, 129756.
1620 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
[8] Wu Y, Wang K-S, Hu Z, Bai B, Shuler P, Tang Y. A new method for fast
screening of long-term thermal stability of water soluble polymers
for reservoir conformance control. In: SPE Improved Oil Recovery
Symp. 2009. p. 1–11, 124257.
[9] Pancharoen M, Thiele MR, Kovscek AR. Inaccessible pore volume of
associative polymer floods. In: SPE Improved Oil Recovery Symp.
2010. p. 1–15, 129910.
[10] Buchgraber M, Clemens T, Castanier LM, Kovscek AR. The displace-
ment of viscous oil by associative polymer solutions. In: SPE Ann
Tech Confr. 2009. p. 1–19, 122400.
[11] Zhang L-J, Yue X-A. Displacement of polymer solution on residual
oil trapped in dead ends. J Cent South Univ Tech 2008;15:84–7.
[12] Zhang L-J, Yue X-A, Guo F. Micro-mechanisms of residual oil mobi-
lization by viscoelastic fluids. Pet Sci 2008;5:56–61.
[13] Wang D, Xia H, Liu Z, Anda Q, Yang Q. Study of the mechanism
of polymer solution with visco-elastic behavior increasing micro-
scopic oil displacement efficiency and the forming of steady “oil
thread” flow channels. In: SPE Asia Pacific Oil Gas Confr. 2001. p.
1–9, 68723.
[14] Yin H, Wang D, Zhong H. Study on flow behaviors of viscoelastic
polymer solution in micropore with dead end. In: SPE Ann Tech
Confr. 2006. p. 1–10, 101950.
[15] Wang D, Cheng J, Yang Q, Gong W, Li Q, Chen F. Viscous-elastic
polymer can increase microscale displacement efficiency in cores.
In: SPE Ann Tech Confr. 2000. p. 1–10, 63227.
[16] Xia H, Ju Y, Kong F, Wu J. Effect of elastic behavior of HPAM solutions
on displacement efficiency under mixed wettability conditions. In:
SPE Ann Tech Confr. 2004. p. 1–8, 90234.
[17] Glass JE, editor. Hydrophilic polymers. Performance with environ-
mental acceptance. Advances in chemistry series 248. Washington,
DC: American Chemical Society; 1996.
[18] Schulz DN, Glass JE, editors. Polymers as rheology modifiers. ACS
symposium series no. 462. Washington, DC: American Chemical
Society; 1991.
[19] Shalaby SW, McCormick CL, Butler GB, editors. Water soluble
polymers. Synthesis, solution properties and applications. ACS
symposium no. 467. Washington, DC: American Chemical Society;
1991.
[20] Glass JE, editor. Polymers in aqueous media: performance through
association. Advances in chemistry series 223. Washington, DC:
American Chemical Society; 1989.
[21] Morgan SE, McCormick CL. Water-soluble polymers in enhanced
oil recovery. Prog Polym Sci 1990;15:103–45.
[22] Sabhapondit A, Borthakur A, Haque I. Characterization of acry-
lamide polymers for enhanced oil recovery. J Appl Polym Sci
2003;87:1869–78.
[23] Sabhapondit A, Borthakur A, Haque I. Water soluble acry-
lamidomethyl propane sulfonate (AMPS) copolymer as an
enhanced oil recovery chemical. Energy Fuels 2003;17:683–8.
[24] Song H, Zhang S-F, Ma X-C, Wang D-Z, Yang J-Z. Synthesis and
application of starch-graft-poly(AM-co-AMPS) by using a complex
initiation system of CS-APS. Carbohydr Polym 2007;69:189–95.
[25] Vega I, Sánchez L, D’Accorso N. Synthesis and characterization of
copolymers with 1,3-oxazolic pendant groups. React Funct Polym
2008;68:233–41.
[26] Borthakur A, Rahman M, Sarmah A, Subrahmanyam B. Partially
hydrolysed polyacrylamide for enhanced oil recovery. Res Ind
1995;40:90–4.
[27] Stokes RJ, Evans DF. Fundamentals of interfacial engineering. New
York: Wiley-VCH; 1997.
[28] Shupe RD. Chemical stability of polyacrylamide polymers. J Pet
Technol 1981;33:1513–29.
[29] Fuoss RM, Strauss UP. Polyelectrolytes. 2. Poly-4-vinylpyridonium
chloride and poly-4-vinyl-N-N-butylpyridonium bromide. J Polym
Sci 1948;3:246–63.
[30] Fuoss RM, Strauss UP. Electrostatic interaction of polyelectrolytes
and simple electrolytes. J Polym Sci 1948;3:602–3.
[31] Fuoss RM. Viscosity function for polyelectrolytes. J Polym Sci
1948;3:603–4.
[32] Ait-Kadi A, Carreau PJ, Chauveteau G. Rheological proper-
ties of partially hydrolyzed polyacrylamide solutions. J Rheol
1987;31:537–61.
[33] Dupuis D, Lewandowski FY, Steiert P, Wolff C. Shear thickening and
time-dependent phenomena: the case of polyacrylamide solutions.
J Non-Newtonian Fluid Mech 1994;54:11–32.
[34] Ellwanger RE, Jaeger DA, Barden RE. Use of the empirical hill equa-
tion for characterization of the effect of added cations on the
viscosity of aqueous solutions of partially hydrolyzed polyacry-
lamide. Polym Bull 1980;3:369–74.
[35] Sukpisan J, Kanatharana J, Sirivat A, Wang Y. The specific viscosity
of partially hydrolyzed polyacrylamide solutions: effects of degree
of hydrolysis, molecular weight, solvent quality and temperature.
J Polym Sci Part B Polym Phys 1998;36:743–53.
[36] Khune GD, Donaruma LG, Hatch MJ, Kilmer NH, Shepitka JS, Martin
FD. Modified acrylamide polymers for enhanced oil recovery. J Appl
Polym Sci 1985;30:875–85.
[37] McCormick CL, Neidlinger HH, Hester RD, Wildman GC. Syn-
thetic random and graft copolymers for utilization in enhanced oil
recovery—synthesis and rheology. In: Shah DO, editor. Surface phe-
nomena in enhanced oil recovery. 1st ed. New York: Plenum; 1981.
p. 741–72.
[38] Dautzenberg H. Polyelectrolyte complex formation in highly aggre-
gating systems. 1. Effect of salt: polyelectrolyte complex formation
in the presence of NaCl. Macromolecules 1997;30:7810–5.
[39] Peng S, Wu C. Light scattering study of the formation and structure
of partially hydrolyzed poly(acrylamide)/calcium(II) complexes.
Macromolecules 1999;32:585–9.
[40] Ohmine I, Tanaka T. Salt effects on the phase transition of ionic gels.
J Chem Phys 1982;77:5725–9.
[41] Ben Jar P-Y, Wu YS. Effect of counter-ions on swelling and shrinkage
of polyacrylamide-based ionic gels. Polymer 1997;38:2557–60.
[42] Cook Jr RL, King HE, Peiffer DG. High-pressure viscosity of
dilute polymer solutions in good solvents. Macromolecules
1992;25:2928–34.
[43] Martin FD, Hatch MJ, Shepitka JS, Ward JS. Improved water-soluble
polymers for enhanced recovery of oil. In: SPE Ann Tech Confr. 1983.
p. 1–14, 11786.
[44] Martin FD. Mechanical degradation of polyacrylamide solutions in
core plugs from several carbonate reservoirs. SPE Formation Eval
1986;1:139–50.
[45] Lewandowska K. Comparative studies of rheological properties of
polyacrylamide and partially hydrolyzed polyacrylamide solutions.
J Appl Polym Sci 2007;103:2235–41.
[46] Hu Y, Wang SQ, Jamieson AM. Rheological and rheooptical stud-
ies of shear-thickening polyacrylamide solutions. Macromolecules
1995;28:1847–53.
[47] Seright RS, Seheult M, Talashek T. Injectivity characteristics of EOR
polymers. SPE Reserv Eval Eng 2009;12:783–92.
[48] Chauveteau G. Molecular interpretation of several different prop-
erties of flow of coiled polymer solutions through porous media
in oil recovery conditions. In: SPE Ann Tech Confr. 1981. p. 1–14,
10060.
[49] Choplin L, Sabatié J. Threshold-type shear-thickening in polymeric
solutions. Rheol Acta 1986;25:570–9.
[50] Ferguson J, Walters K, Wolff C. Shear and extensional flow of poly-
acrylamide solutions. Rheol Acta 1990;29:571–9.
[51] Shepitka JS, Case CE, Donaruma LG, Hatch MJ, Kilmer NH, Khune GD,
Martin FD, Ward JS, Wilson KV. Partially imidized, water-soluble
polymeric amides. 1. Partially imidized polyacrylamide and poly-
methacrylamide. J Appl Polym Sci 1983;28:3611–7.
[52] Durst F, Haas R, Interthal W. The nature of flows through porous
media. J Non-Newtonian Fluid Mech 1987;22:169–89.
[53] James D, MacLaren DR. Laminar-flow of dilute polymer-solutions
through porous media. J Fluid Mech 1975;70:733–52.
[54] Magueur A, Moan M, Chauveteau G. Effect of successive contrac-
tions and expansions on the apparent viscosity of dilute polymer
solutions. Chem Eng Commun 1985;36:351–66.
[55] Silberberg A, Mijnlieff PF. Study of reversible gelation of partially
neutralized poly(methacrylic acid) by viscoelastic measurements.
J Polym Sci Part A2 Polym Phys 1970;8:1089.
[56] Quadrat O. Negative thixotropy in polymer solutions. Adv Colloid
Interface Sci 1985;24:45–75.
[57] Ohya S, Matsuo T. Time-dependent change of viscosity in poly-
methacrylic acid solution. J Colloid Interface Sci 1979;68:593–5.
[58] Bradna P, Quadrat O, Dupuis D. The influence of salt concentra-
tion on negative thixotropy in solutions of partially hydrolyzed
polyacrylamide. Colloid Polym Sci 1995;273:421–5.
[59] Quadrat O, Bradna P, Dupuis D, Wolff C. Negative thixotropy of solu-
tions of partially hydrolyzed polyacrylamide. Part I. The influence
of shear rate on time changes of flow characteristics. Colloid Polym
Sci 1992;270:1057–9.
[60] Bradna P, Quadrat O, Dupuis D. Negative thixotropy of solu-
tions of partially hydrolyzed polyacrylamide. Part II. The influence
of glycerol content and degree of ionization. Colloid Polym Sci
1995;273:642–7.
[61] Bradna P, Quadrat O, Titkova L, Dupuis D. The influence of multiva-
lent cations on negative thixotropy in aqueous glycerol solutions of
partially hydrolyzed polyacrylamide. Acta Polym 1997;48:446–9.
 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
[62] Ghannam MT, Esmail MN. Rheological properties of aqueous poly-
acrylamide solutions. J Appl Polym Sci 1998;69:1587–97.
[63] Xin X, Xu G, Gong H, Bai Y, Tan Y. Interaction between sodium oleate
and partially hydrolyzed polyacrylamide: a rheological study. Col-
loids Surf A 2008;326:1–9.
[64] Methemitis C, Morcellet M, Sabbadin J, Francois J. Interactions
between partially hydrolyzed polyacrylamide and ionic surfac-
tants. Eur Polym J 1986;22:619–27.
[65] Leela JK, Sharma G. Studies on xanthan production from Xan-
thomonas campestris. Bioprocess Eng 2000;23:687–9.
[66] Nasr S, Soudi MR, Haghighi M. Xanthan production by a native
strain of X. campestris and evaluation of application in EOR. Pak
J Biol Sci 2007;10:3010–3.
[67] García-Ochoa F, Santos VE, Casas JA, Gómez E. Xanthan gum: pro-
duction, recovery, and properties. Biotechnol Adv 2000;18:549–79.
[68] Becker A, Katzen F, Puhler A, Ielpi L. Xanthan gum biosynthesis
and application: a biochemical/genetic perspective. Appl Environ
Microbiol 1998;50:145–52.
[69] Morris ER, Rees DA, Young G, Walkinshaw MD, Darke A.
Order–disorder transition for a bacterial polysaccharide in
solution—role for polysaccharide conformation in recognition
between Xanthomonas pathogen and its plant host. J Mol Biol
1977;110:1–16.
[70] Dentini M, Crescenzi V, Blasi D. Conformational properties of xan-
than derivatives in dilute aqueous-solution. Int J Biol Macromol
1984;6:93–8.
[71] Norton IT, Goodall DM, Frangou SA, Morris ER, Rees DA. Mechanism
and dynamics of conformational ordering in xanthan polysaccha-
ride. J Mol Biol 1984;175:371–94.
[72] Holzwarth G. Conformation of extracellular polysaccharide of
Xanthomonas-campestris. Biochemistry 1976;15:4333–9.
[73] Chen CSH, Sheppard EW. Conformation and shear stability of xan-
than gum in solution. Polym Eng Sci 1980;20:512–6.
[74] Yoshida T, Tanner RD, editors. Bioproducts and bioprocess. Berlin:
Springer-Verlag; 1993.
[75] Richardson RK, Rossmurphy SB. Nonlinear viscoelasticity of
polysaccharide solutions. 2. Xanthan polysaccharide solutions. Int
J Biol Macromol 1987;9:257–64.
[76] Kierulf C, Sutherland IW. Thermal-stability of xanthan prepara-
tions. Carbohydr Polym 1988;9:185–94.
[77] Lambert F, Rinaudo M. On the thermal-stability of xanthan gum.
Polymer 1985;26:1549–53.
[78] Seright RS, Henrici BJ. Xanthan stability at elevated temperatures.
SPE Reserv Eng 1990;1:52–60.
[79] Wellington SL. Bio-polymer solution viscosity stabilization—
polymer degradation and antioxidant use. Soc Pet Eng J
1983;23:901–12.
[80] Ash SG, Clarke-Sturman AJ, Calvert R, Nisbet TM. Chemical stabil-
ity of biopolymer solutions. In: SPE Ann Tech Confr. 1983. p. 1–8,
12085.
[81] Sutherland IW. An enzyme system hydrolysing the polysaccharides
of Xanthomonas species. J Appl Bacteriol 1982;53:385–93.
[82] Cadmus MC, Jackson LK, Burton KA, Plattner RD, Slodki ME.
Biodegradation of xanthan gum by Bacillus sp. Appl Environ Micro-
biol 1982;44:5–11.
[83] Bragg JR, Maruca SD, Gale WW, Gall LS, Wernau WC, Beck D,
Goldman IM, Laskin AI, Naslund LA. Control of xanthan-degrading
organisms in the loudon pilot: approach, methodology, and results.
In: SPE Ann Tech Confr. 1983. p. 1–12, 11989.
[84] Hou CT, Barnabe N, Greaney K. Biodegradation of xanthan by salt-
tolerant aerobic microorganisms. J Ind Microbiol 1986;1:31–7.
[85] Taugbol K, Ly TV, Austad T. Chemical flooding of oil-reservoirs. 3.
Dissociative surfactant–polymer interaction with a positive effect
on oil-recovery. Colloids Surf A 1995;103:83–90.
[86] Austad T, Taugbol K. Chemical flooding of oil-reservoirs. 2. Disso-
ciative surfactant–polymer interaction with a negative effect on
oil-recovery. Colloids Surf A 1995;103:73–81.
[87] Taylor KC, Nasr-El-Din HA. Water-soluble hydrophobically associ-
ating polymers for improved oil recovery: a literature review. J Pet
Sci Eng 1998;19:265–80.
[88] Hill A, Candau F, Selb J. Properties of hydrophobically associating
polyacrylamides: influence of the method of synthesis. Macro-
molecules 1993;26:4521–32.
[89] Annable T, Buscall R, Ettelaie R, Whittlestone D. The rheology
of solutions of associating polymer: comparison of experimental
behavior with transient network theory. J Rheol 1993;37:695–726.
[90] Panmai S, Prud’homme RK, Peiffer DG. Rheology of hydrophobically
modified polymers with spherical and rod-like surfactant micelles.
Colloids Surf A 1999;147:3–15.
1621
[91] English RJ, Laurer JH, Spontak RJ, Khan SA. Hydrophobically
modified associative polymer solutions: rheology and microstruc-
ture in the presence of nonionic surfactants. Ind Eng Chem Res
2002;41:6425–35.
[92] Biggs S, Selb J, Candau F. Effect of surfactant on the solution
properties of hydrophobically modified polyacrylamide. Langmuir
1992;8:838–47.
[93] Sarkar N, Kershner LD. Rigid rod water-soluble polymers. J Appl
Polym Sci 1996;62:393–408.
[94] Maia AMS, Borsali R, Balaban RC. Comparison between a polyacry-
lamide and a hydrophobically modified polyacrylamide flood in a
sandstone core. Mater Sci Eng C 2009;29:505–9.
[95] Dubin PL, Strauss UP. Hydrophobic bonding in alternating copoly-
mers of maleic acid and alkyl vinyl ethers. J Phys Chem
1970;74:2842–7.
[96] Dubin PL, Strauss UP. Hydrophobic hypercoiling in copolymers of
maleic acid and alkyl vinyl ethers. J Phys Chem 1967;71:2757–9.
[97] Schwab FC, Sheppard EW, Chen CSH. Waterflooding process
employing cationic-nonionic copolymers. US Pat 4,110,232; 1978.
[98] Landoll LM. Hydrophobically modified polymers. US Pat 4,529,523;
1984.
[99] Bock J, Pace SJ, Schulz DN. Enhanced oil recovery with hydropho-
bically associating polymers containing N-vinyl pyrrolidone
functionality. US Pat 4,709,759; 1987.
[100] Bock J, Valint PL, Pace SJ. Enhanced oil recovery with hydropho-
bically associating polymers containing sulfonate functionality. US
Pat 4,702,319; 1987.
[101] Bock J, Siano DB, Pace SJ. Enhanced oil recovery with hydrophobi-
cally associating polymers. Can Pat 1300362; 1992.
[102] Evani S. Enhanced oil recovery process using a hydrophobic associa-
tive composition containing a hydrophilic/hydrophobic polymer.
US Pat 4,814,096; 1989.
[103] McCormick CL, Nonaka T, Johnson CB. Water-soluble copolymers.
27. Synthesis and aqueous solution behavior of associa-
tive acrylamide/N-alkylacrylamide copolymers. Polymer
1988;29:731–9.
[104] Lara-Ceniceros AC, Rivera-Vallejo C, Jimenez-Regalado EJ. Synthe-
sis, characterization and rheological properties of three different
associative polymers obtained by micellar polymerization. Polym
Bull 2007;58:425–33.
[105] Tam KC, Jenkins RD, Winnik MA, Bassett DR. A structural model of
hydrophobically modified urethane-ethoxylate (HEUR) associative
polymers in shear flows. Macromolecules 1998;31:4149–59.
[106] Tam KC, Seng WP, Jenkins RD, Bassett DR. Rheological and
microcalorimetric studies of a model alkali-soluble associative
polymer (HASE) in nonionic surfactant solutions. J Polym Sci Part B
Polym Phys 2000;38:2019–32.
[107] Feng Y, Billon L, Grassl B, Khoukh A, François J. Hydrophobi-
cally associating polyacrylamides and their partially hydrolyzed
derivatives prepared by post modification. 1. Synthesis and char-
acterization. Polymer 2002;43:2055–64.
[108] Argillier J-F, Audibert A, Lecourtier J, Moan M, Rousseau L. Solution
and adsorption properties of hydrophobically associating water-
soluble polyacrylamides. Colloids Surf A 1996;113:247–57.
[109] Volpert E, Selb J, Candau F. Influence of the hydrophobe structure on
composition, microstructure, and rheology in associating polyacry-
lamides prepared by micellar copolymerization. Macromolecules
1996;29:1452–63.
[110] Ezzell SA, McCormick CL. Water-soluble copolymers. 39. Synthe-
sis and solution properties of associative acrylamido copolymers
with pyrenesulfonamide fluorescence labels. Macromolecules
1992;25:1881–6.
[111] Ezzell SA, Hoyle CE, Creed D, McCormick CL. Water-soluble
copolymers. 40. Photophysical studies of the solution behavior
of associative pyrenesulfonamide-labeled polyacrylamides. Macro-
molecules 1992;25:1887–95.
[112] Klucker R, Candau F, Schosseler F. Transient behavior of associating
copolymers in shear flow. Macromolecules 1995;28:6416–22.
[113] Dowling KC, Thomas JK. A novel micellar synthesis and photophys-
ical characterization of water-soluble acrylamide–styrene block
copolymers. Macromolecules 1990;23:1059–64.
[114] Schulz DN, Kaladas JJ, Maurer JJ, Bock J, Pace SJ, Schulz WW. Copoly-
mers of acrylamide and surfactant macromonomers: synthesis and
solution properties. Polymer 1987;28:2110–5.
[115] Peiffer DG. Hydrophobically associating polymers and their inter-
actions with rod-like micelles. Polymer 1990;31:2353–60.
[116] Iliopoulos I, Wang TK, Audebert R. Viscometric evidence of inter-
actions between hydrophobically modified poly(sodium acrylate)
and sodium dodecyl sulfate. Langmuir 1991;7:617–9.
1622 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
[117] Senan C, Meadows J, Shone PT, Williams PA. Solution behav-
ior of hydrophobically modified sodium polyacrylate. Langmuir
1994;10:2471–9.
[118] Tanaka R, Meadows J, Williams PA, Phillips GO. Interaction of
hydrophobically modified (hydroxyethyl)cellulose with various
added surfactants. Macromolecules 1992;25:1304–10.
[119] Winnik FM. Association of hydrophobic polymers in water:
fluorescence studies with labeled (hydroxypropyl)celluloses.
Macromolecules 1989;22:734–42.
[120] Durand A, Hourdet D. Synthesis and thermoassociative properties
in aqueous solution of graft copolymers containing poly(N-
isopropylacrylamide) side chains. Polymer 1999;40:4941–51.
[121] Maia AMS, Costa M, Borsali R, Garcia RB. Rheological behavior
and scattering studies of acrylamide-based copolymer solutions.
Macromol Symp 2005;229:217–27.
[122] Lundberg DJ, Brown RG, Glass JE, Eley RR. Synthesis, characteri-
zation, and solution rheology of model hydrophobically-modified,
water-soluble ethoxylated urethanes. Langmuir 1994;10:3027–34.
[123] Winnik MA, Yekta A. Associative polymers in aqueous solution. Curr
Opin Colloid Interface Sci 1997;2:424–36.
[124] Huldén M. Hydrophobically modified urethane-ethoxylate (HEUR)
associative thickeners. 1. Rheology of aqueous solutions and inter-
actions with surfactants. Colloids Surf A 1994;82:263–77.
[125] Xu B, Li L, Zhang K, MacDonald PM, Winnik MA, Jenkins R, Bas-
set D, Wolf D, Nuyken O. Synthesis and characterization of comb
associative polymers based on poly(ethylene oxide). Langmuir
1997;13:6896–902.
[126] Rao B, Uemura Y, Dyke L, Mcdonald PM. Self-diffusion coefficients
of hydrophobic ethoxylated urethane associating polymers using
pulsed-gradient spin-echo nuclear magnetic resonance. Macro-
molecules 1995;28:531–8.
[127] Alami E, Almgren M, Brown W. Interaction of hydrophobically
end-capped poly(ethylene oxide) with nonionic surfactants in
aqueous solution. Fluorescence and light scattering studies. Macro-
molecules 1996;29:5026–35.
[128] Alami E, Almgren M, Brown W. Aggregation of hydropho-
bically end-capped poly(ethylene oxide) in aqueous solu-
tions. Fluorescence and light-scattering studies. Macromolecules
1996;29:2229–43.
[129] Yekta A, Duhamel J, Brochard P, Adiwidjaja H, Winnik MA. A
fluorescent probe study of micelle-like cluster formation in aque-
ous solutions of hydrophobically modified poly(ethylene oxide).
Macromolecules 1993;26:1829–36.
[130] Maechling-Strasser C, Clouet F, Francois J. Hydrophobically
end-capped polyethylene-oxide urethanes: 2. Modelling their
association in water. Polymer 1992;33:1021–5.
[131] Maechling-Strasser C, Francois J, Clouet F. Hydrophobically end-
capped poly(ethylene oxide) urethanes. 1. Characterization and
experimental study of their association in aqueous solution. Poly-
mer 1992;33:627–36.
[132] Xie X, Hogen-Esch TE. Copolymers of N,N-dimethylacrylamide
and 2-(N-ethylperfluorooctanesulfonamido)ethyl acrylate in aque-
ous media and in bulk. Synthesis and properties. Macromolecules
1996;29:1734–45.
[133] Abu-Sharkh BF, Yahaya GO, Ali SA, Kazi IW. Solution and interfacial
behavior of hydrophobically modified water-soluble block copoly-
mers of acrylamide and N-phenethylacrylamide. J Appl Polym Sci
2001;82:467–76.
[134] Volpert E, Selb J, Candau F. Associating behaviour of poly-
acrylamides hydrophobically modified with dehexylacrylamide.
Polymer 1998;39:1025–33.
[135] Candau F, Selb J. Hydrophobically-modified polyacrylamides pre-
pared by micellar polymerization. Adv Colloid Interface Sci
1999;79:149–72.
[136] Yahya GO, Ali SA, Alnaafa MA, Hamad EZ. Preparation and viscosity
behavior of hydrophobically-modified poly(vinyl alcohol) (PVA). J
Appl Polym Sci 1995;57:343–52.
[137] Yahya GO, Hamad EZ. Solution behaviour of sodium maleate/1-
alkene copolymers. Polymer 1995;36:3705–10.
[138] Kopperud HM, Hansen FH, Nyström B. Effect of surfactant and
temperature on the rheological properties of aqueous solutions of
unmodified and hydrophobically modified polyacrylamide. Macro-
mol Chem Phys 1998;199:2385–94.
[139] Shaikh S, Asrof Ali SK, Hamad EZ, Abu-Sharkh BF. Synthesis
and solution properties of poly(acrylamide-styrene) block copoly-
mers with high hydrophobic content. Polym Eng Sci 1999;39:
1962–8.
[140] Hourdet D, Gadgil J, Podhajecka K, Badiger MV, Brûlet A,
Wadgaonkar PP. Thermoreversible behavior of associating poly-
mer solutions: thermothinning versus thermothickening. Macro-
molecules 2005;38:8512–21.
[141] Mortensen K, Brown W, JØrgensen E. Phase behavior
poly(propylene oxide)–poly(ethylene oxide)–poly(propylene
oxide) triblock copolymer melt and aqueous solutions.
Macromolecules 1994;27:5654–66.
[142] Nishinari K, Hofmann KE, Moritaka H, Kohyama K, Nishinari
N. Gel–sol transition of methylcellulose. Macromol Chem Phys
1997;198:1217–26.
[143] Doelker E. Cellulose derivatives. Adv Polym Sci 1993;107:199–265.
[144] Sarkar N. Thermal gelation properties of methyl and hydroxypropyl
methylcellulose. J Appl Polym Sci 1979;24:1073–87.
[145] Yoshioka H, Mikami M, Mori Y, Tsuchida E. A synthetic hydro-
gel with thermoreversible gelation. 1. Preparation and rheological
properties. J Macromol Sci Part A Pure Appl Chem 1994;31:
113–20.
[146] Nyström B, Walderhaug H, Hansen FK. Dynamic light scat-
tering and rheological studies of thermoreversible gelation
of a poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene
oxide) triblock copolymer in aqueous solution. Faraday Discuss
1995;101:335–44.
[147] Wang G, Lindell K, Olofsson G. On the thermal gelling of
ethyl(hydroxyethyl)cellulose and sodium dodecyl sulfate. Phase
behavior and temperature scanning calorimetric response. Macro-
molecules 1997;30:105–12.
[148] Loyen K, Iliopoulos I, Audebert R, Olsson U. Reversible thermal
gelation in polymer/surfactant systems. Control of the gelation
temperature. Langmuir 1995;11:1053–6.
[149] Sarrazin-Cartalas A, Iliopoulos I, Audebert R, Olsson U. Associa-
tion and thermal gelation in mixtures of hydrophobically modified
polyelectrolytes and nonionic surfactants. Langmuir 1994;10:
1421–6.
[150] Greenhill-Hooper MJ, O’Sullivan TP, Wheele PA. The aggrega-
tion behavior of octadecylphenylalkoxysulfonates. 1. Temperature
dependence of the solution behavior. J Colloid Interface Sci
1988;124:77–87.
[151] Bokias G, Hourdet D, Iliopoulos I, Staikos G, Audebert R.
Hydrophobic interactions of poly(N-isopropylacrylamide) with
hydrophobically modified poly(sodium acrylate) in aqueous solu-
tion. Macromolecules 1997;30:8293–7.
[152] Hourdet D, L’Alloret F, Audebert R. Synthesis of thermoassociative
copolymers. Polymer 1997;38:2535–47.
[153] Hourdet D, L’Alloret F, Audebert R. Reversible thermothickening of
aqueous polymer solutions. Polymer 1994;35:2624–30.
[154] de Vos S, Möller M, Visscher K, Mijnlieff PF. Synthesis and
characterization of poly(acrylamide)-graft-poly(ethylene oxide-
co-propylene oxide). Polymer 1994;35:2644–50.
[155] Hutchinson BH, McCormick CL. Water-soluble copolymers. 15.
Studies of random copolymers of acrylamide with N-substituted
acrylamides by C-13 NMR. Polymer 1986;27:623–6.
[156] Magny B, Lafuma F, Iliopoulos I. Determination of microstructure
of hydrophobically modified water-soluble polymers by C-13 NMR.
Polymer 1992;33:3151–4.
[157] Newman JK, McCormick CL. Water-soluble copolymers. 51.
Copolymer compositions of high-molecular-weight functional
acrylamido water-soluble polymers using direct-polarization
magic-angle-spinning C-13 nuclear-magnetic-resonance. Polymer
1994;35:935–8.
[158] McCormick CL, Chen GS, Hutchinson BH. Water-soluble copoly-
mers. 5. Compositional determination of random copolymers
of acrylamide with sulfonated co-monomers by infrared-
spectroscopy and C-13 nuclear magnetic-resonance. J Appl Polym
Sci 1982;27:3103–20.
[159] Newman JK, McCormick CL. Water-soluble copolymers. 53. Na-23
NMR-studies of hydrophobically-modified polyacids—copolymers
of 2-(1-naphthylacetamido)ethylacrylamide with acrylic-acid and
methacrylic-acid. Macromolecules 1994;27:5123–8.
[160] Newman JK, McCormick CL. Water-soluble copolymers. 52. Na-
23 NMR-studies of ion-binding to anionic polyelectrolytes—poly-
(sodium 2-acrylamido-2-methylpropanesulfonate), poly(sodium
3-acrylamido-3-methylbutanoate), poly(sodium acrylate), and
poly(sodium galacturonate). Macromolecules 1994;27:5114–22.
[161] Furo I, Iliopoulos I, Stilbs P. Structure and dynamics of associative
water-soluble polymer aggregates as seen by F-19 NMR spec-
troscopy. J Phys Chem B 2000;104:485–94.
[162] Walderhaug H, Hansen FK, Abrahmsen S, Persson K, Stilbs P. Asso-
ciative thickeners—NMR self-diffusion and rheology studies of
aqueous-solutions of hydrophobically-modified poly(oxyethylene)
polymers. J Phys Chem 1993;97:8336–42.
 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
[163] Nystrom B, Walderhaug H, Hansen FK. Dynamic crossover effects
observed in solutions of a hydrophobically associating water-
soluble polymer. J Phys Chem 1993;97:7743–52.
[164] Abrahmsén-Alami S, Stilbs P. 1 H NMR self-diffusion and multi-
field 2H spin relaxation study of model associative polymer and
sodium dodecyl sulfate aggregation in aqueous solution. J Phys
Chem 1994;98:6359–67.
[165] Persson K, Abrahmsen S, Stilbs P, Hansen FK, Walderhaug H. The
association of urethane-polyethyleneoxide (Heur) thickeners. As
studied by NMR self-diffusion measurements. Colloid Polym Sci
1992;270:465–9.
[166] McCormick CL, Elliott DL. Water-soluble copolymers. 14. Potentio-
metric and turbidimetric studies of water-soluble copolymers of
acrylamide—comparison of carboxylated and sulfonated copoly-
mers. Macromolecules 1986;19:542–7.
[167] Wang C, Tam KC, Jenkins RD, Bassett DR. Potentiometric titration
and dynamic light scattering of hydrophobically modified alkali sol-
uble emulsion (HASE) polymer solutions. Phys Chem Chem Phys
2000;2:1967–72.
[168] Wang C, Tam KC, Jenkins RD. Dissolution behavior of HASE poly-
mers in the presence of salt: potentiometric titration, isothermal
titration calorimetry, and light scattering studies. J Phys Chem B
2002;106:1195–204.
[169] Dai S, Tam KC, Jenkins RD, Bassett DR. Light scattering of
dilute hydrophobically modified alkali-soluble emulsion solutions:
effects of hydrophobicity and spacer length of macromonomer.
Macromolecules 2000;33:7021–8.
[170] Chassenieux C, Nicolai T, Durand D. Association of hydropho-
bically end-capped poly(ethylene oxide). Macromolecules
1997;30:4952–8.
[171] Prochazka K, Martin TJ, Webber SE, Munk P. Onion-type micelles in
aqueous media. Macromolecules 1996;29:6526–30.
[172] Prochazka K, Martin TJ, Munk P, Webber SE. Polyelectrolyte
poly(tert-butyl acrylate)-block-poly(2-vinylpyridine) micelles in
aqueous media. Macromolecules 1996;29:6518–25.
[173] Biggs S, Selb J, Candau F. Copolymers of acrylamide/N-
alkylacrylamide in aqueous solution: the effects of hydrolysis on
hydrophobic interactions. Polymer 1993;34:580–91.
[174] Biggs S, Hill A, Selb J, Candau F. Copolymerization of acrylamide
and a hydrophobic monomer in an aqueous medium: effect of
the surfactant on the copolymer microstructure. J Phys Chem
1992;96:1505–11.
[175] Branham KD, Davis DL, Middleton JC, McCormick CL. Water-soluble
polymers. 59. Investigation of the effects of polymer microstructure
on the associative behaviour of amphiphilic terpolymers of acry-
lamide, acrylic acid and N-[(4-decyl)phenyl]acrylamide. Polymer
1994;35:4429–36.
[176] Branham KD, Snowden HS, McCormick CL. Water-soluble copoly-
mers. 64. Effects of pH and composition on associative properties
of amphiphilic acrylamide/acryl acid terpolymers. Macromolecules
1996;29:254–62.
[177] Branham KD, Shafer GS, Hoyle CE, McCormick CL. Water-
soluble copolymers. 61. Microstructural investigation of
pyrenesulfonamide-labeled polyelectrolytes. Variation of label
proximity utilizing micellar polymerization. Macromolecules
1995;28:6175–82.
[178] Kramer MC, Steger JR, Hu Y, McCormick CL. Water-soluble
copolymers. 65. Environmentally responsive associations probed
by nonradiative energy transfer studies of naphthalene and
pyrene-labeled poly(acrylamide-co-sodium 11-(acrylamido)-
undecanoate). Macromolecules 1996;29:1992–7.
[179] Kramer MC, Welch CG, Steger JR, McCormick CL. Water-soluble
copolymers. 63. Rheological and photophysical studies on the asso-
ciative properties of pyrene-labeled poly[acrylamide-co-sodium
11-(acrylamido)undecanoate]. Macromolecules 1995;28:5248–54.
[180] Araujo E, Rharbi Y, Huang X, Winnik MA, Bassett DR, Jenkins RD.
Pyrene excimer kinetics in micelle like aggregates in a 0-HASE
associating polymer. Langmuir 2000;16:8664–71.
[181] Kumacheva E, Rharbi Y, Winnik MA, Guo L, Tam KC, Jenkins RD.
Fluorescence studies of an alkaline swellable associative polymer
in aqueous solution. Langmuir 1997;13:182–6.
[182] Rufier C, Collet A, Viguier M, Oberdisse J, Mora S. SDS interactions
with hydrophobically end-capped poly(ethylene oxide) studied by
13
C NMR and SANS. Macromolecules 2009;42:5226–35.
[183] Hu Y, Kramer MC, Boudreaux CJ, McCormick CL. Water-soluble
copolymers. 62. Nonradiative energy-transfer studies of pH-
responsive and salt-responsive associations in hydrophobically-
modified, hydrolyzed maleic anhydride-ethyl vinyl ether copoly-
mers. Macromolecules 1995;28:7100–6.
1623
[184] Hu YX, Smith GL, Richardson MF, McCormick CL. Water sol-
uble polymers. 74. pH responsive microdomains in labeled
n-octylamide-substituted poly(sodium maleate-alt-ethyl
vinyl ethers): synthesis, steady-state fluorescence, and non-
radiative energy transfer studies. Macromolecules 1997;30:
3526–37.
[185] Smith GL, McCormick CL. Water-soluble polymers. 78. Viscosity and
NRET fluorescence studies of pH-responsive twin-tailed associative
terpolymers based on acrylic acid and methacrylamide. Macro-
molecules 2001;34:918–24.
[186] Cathébras N, Collet A, Viguier M, Berret J-F. Synthesis and linear vis-
coelasticity of fluorinated hydrophobically modified ethoxylated
urethanes (F-HEUR). Macromolecules 1998;31:1305–11.
[187] Kaczmarski JP, Glass JE. Synthesis and solution properties
of hydrophobically-modified ethoxylated urethanes with vari-
able oxyethylene spacer lengths. Macromolecules 1993;26:
5149–56.
[188] May R, Kaczmarski JP, Glass JE. Influence of molecular weight dis-
tributions on HEUR aqueous solution rheology. Macromolecules
1996;29:4745–53.
[189] Zhang HS, Pan J, Hogen-Esch TE. Synthesis and characteriza-
tion of one-ended perfluorocarbon-functionalized derivatives of
poly(ethylene glycol)s. Macromolecules 1998;31:2815–21.
[190] McCormick CL, Hester RD, Morgan SE, Safieddine AM. Water-
soluble copolymers. 31. Effects of molecular-parameters, solvation,
and polymer associations on drag reduction performance. Macro-
molecules 1990;23:2132–9.
[191] McCormick CL, Hester RD, Morgan SE, Safieddine AM. Water-
soluble copolymers. 30. Effects of molecular-structure on drag
reduction efficiency. Macromolecules 1990;23:2124–31.
[192] McCormick CL, Blackmon KP. Water-soluble copolymers.
21. Copolymers of acrylamide with 2-acrylamido-2-
methylpropanedimethylammonium chloride: synthesis and
characterization. Polymer 1986;27:1971–5.
[193] McCormick CL, Blackmon KP, Elliot DL. Water-soluble copoly-
mers. 22. Copolymers of acrylamide with 2-acrylamido-2-
methylpropanedimethylammonium chloride: aqueous solution
properties of a polycation. Polymer 1986;27:1976–80.
[194] McCormick CL, Blackmon KP. Water-soluble copolymers. 17.
Copolymers of acrylamide with sodium 3-methacrylamido-3-
methylbutanoate: synthesis and characterization. Macromolecules
1986;19:1512–5.
[195] McCormick CL, Elliot DL, Blackmon KP. Water-soluble copolymers.
18. Copolymers of acrylamide with sodium 3-methacrylamido-3-
methylbutanoate: microstructural studies and solution properties.
Macromolecules 1986;19:1516–22.
[196] Kathmann EE, White LA, McCormick CL. Water-soluble polymers.
73. Electrolyte- and pH-responsive zwitterionic copolymers
of 4-[(2-acrylamido-2-methylpropyl)-dimethylammonio]-
butanoate with 3-[(2-acrylamido-2-methylpropyl)dimethyl-
ammonio]propanesulfonate. Macromolecules 1997;30:5297–304.
[197] McCormick CL, Salazar LC. Water soluble copolymers. 46.
Hydrophilic sulphobetaine copolymers of acrylamide and
3-(2-acrylamido-2-methylpropanedimethyl-ammonio)-1-
propanesulphonate. Polymer 1992;33:4617–24.
[198] Kathmann EE, White LA, McCormick CL. Water soluble polymers.
69. pH and electrolyte responsive copolymers of acrylamide and the
zwitterionic monomer 4-(2-acrylamido-2-methylpropyldimethyl-
ammonio) butanoate: synthesis and solution behaviour. Polymer
1997;38:871–8.
[199] Kathmann EE, White LA, McCormick CL. Water soluble polymers.
70. Effects of methylene versus propylene spacers in the pH and
electrolyte responsiveness of zwitterionic copolymers incorporat-
ing carboxybetaine monomers. Polymer 1997;38:879–86.
[200] Kathmann EE, McCormick CL. Water-soluble polymers. 72.
Synthesis and solution behavior of responsive copolymers of
acrylamide and the zwitterionic monomer 6-(2-acrylamido-2-
methylpropyldimethylammonio) hexanoate. J Polym Sci Part A
Polym Chem 1997;35:243–53.
[201] Kathmann EEL, Davis DD, McCormick CL. Water-soluble poly-
mers. 60. Synthesis and solution behavior of terpolymers of acrylic
acid, acrylamide and the zwitterionic monomer 3-[(2-acrylamido-
2-methylpropyl)dimethylammonio]-1-propanesulfonate. Macro-
molecules 1994;27:3156–61.
[202] Kathmann EE, McCormick CL. Water-soluble polymers. 71.
pH responsive behavior of terpolymers of sodium acrylate,
acrylamide, and the zwitterionic monomer 4-(2-acrylamide-2-
methylpropanedimethylammonio)butanoate. J Polym Sci Part A
Polym Chem 1997;35:231–42.
1624 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
[203] Grassl B, Francois J, Billon L. Associating behaviour of polyacry-
lamide modified with a new hydrophobic zwitterionic monomer.
Polym Int 2001;50:1162–9.
[204] McCormick CL, Johnson CB. Water-soluble polymers: 33.
Ampholytic terpolymers of sodium 2-acrylamido-2-methylpro-
panesulphonate with 2-acrylamido-2-methylpropanedimethy-
lammonium chloride and acrylamide: Synthesis and aqueous
solution behaviour. Polymer 1990;31:1100–7.
[205] Mumick PS, Welch PM, Salazar LC, McCormick CL. Water-soluble
copolymers. 56. Structure and solvation effects of polyampholytes
in drag reduction. Macromolecules 1994;27:323–31.
[206] Mumick PS. Structurally tailored water soluble polymers for the
study of drag reduction. PhD Dissertation, Hattiesburg MS: The
University of Southern Mississippi; 1993.
[207] Salazar LC. Synthesis and solution behavior of electrolyte-
responsive polyampholytes. PhD Dissertation, Hattiesburg MS: The
University of Southern Mississippi; 1991.
[208] McCormick CL, Johnson CB. Water-soluble polymers.
XXXIV. Ampholytic terpolymers of sodium 3-acrylamido-3-
methylbutanoate with 2-acrylamido-2-methylpropanedimethyl-
ammonium chloride and acrylamide: synthesis and absorbancy
behavior. J Macromol Sci Part A Pure Appl Chem 1990;27:539–47.
[209] McCormick CL, Johnson CB. Water-soluble copolymers.
29. Ampholytic copolymers of sodium 2-acrylamido-2-
methylpropanesulfonate with (2-acrylamido-2-methylpropyl)-
dimethylammonium chloride: solution properties. Macro-
molecules 1988;21:694–9.
[210] McCormick CL, Johnson CB. Water-soluble polymers. 28.
Ampholytic copolymers of sodium 2-acrylamido-2-methyl-
propanesulfonate with (2-acrylamido-2-methylpropyl)-
dimethylammonium chloride: synthesis and characterization.
Macromolecules 1988;21:686–93.
[211] McCormick CL, Salazar LC. Water-soluble copolymers. 43.
Ampholytic copolymers of sodium 2-(acrylamido)-2-methyl-
propanesulfonate with[2-(acrylamido)-2-methylpropyl]trimethy-
lammonium chloride. Macromolecules 1992;25:1896–900.
[212] Petit F, Iliopoulos I, Audebert R, Szonyi S. Associating polyelec-
trolytes with perfluoroalkyl side chains: aggregation in aqueous
solution, association with surfactants, and comparison with hydro-
genated analogues. Langmuir 1997;13:4229–33.
[213] Shedge AS, Lele AK, Wadgaonkar PP, Hourdet D, Pcrrin P, Chas-
senieux C, Badiger MV. Hydrophobically modified poly(acrylic
acid) using 3-pentadecylcyclohexylamine: synthesis and rheology.
Macromol Chem Phys 2005;206:464–72.
[214] Tomatsu I, Hashidzume A, Yusa S, Morishima Y. Unique associative
properties of copolymers of sodium acrylate and oligo(ethylene
oxide) alkyl ether methacrylates in water. Macromolecules
2005;38:7837–44.
[215] Noda T, Hashidzume A, Morishima Y. Effects of spacer length
on the side-chain micellization in random copolymers of
sodium 2-(acrylamido)-2-methylpropanesulfonate and methacry-
lates substituted with ethylene oxide-based surfactant moieties.
Macromolecules 2001;34:1308–17.
[216] Noda T, Hashidzume A, Morishima Y. Rheological properties of
transient networks formed from copolymers of sodium acry-
late and methacrylates substituted with amphiphiles: comparison
with sodium 2-(acrylamido)-2-methylpropanesulfonate copoly-
mers. Langmuir 2001;17:5984–91.
[217] Zhong C, Luo P, Ye Z, Chen H. Characterization and solution proper-
ties of a novel water-soluble terpolymer for enhanced oil recovery.
Polym Bull 2009;62:79–89.
[218] Smith GL, McCormick CL. Water-soluble polymers. 80. Rheo-
logical and photophysical studies of pH-responsive terpolymers
containing hydrophobic twin-tailed acrylamide monomers. Macro-
molecules 2001;34:5579–86.
[219] McCormick CL, Hoyle CE, Clark MD. Water-soluble copolymers.
26. Fluorescence probe studies of hydrophobically modified maleic
acid–ethyl vinyl ether copolymers. Polymer 1992;33:243–7.
[220] Chang Y, McCormick CL. Water-soluble copolymers. 49. Effect
of the distribution of the hydrophobic cationic monomer
dimethyldodecyl(2-acrylamidoethyl)ammonium bromide on the
solution behavior of associating acrylamide copolymers. Macro-
molecules 1993;26:6121–6.
[221] Zhuang DQ, Da JCAH, Zhang YX, Dieing R, Ma L, Haeussling L.
Hydrophobically modified polyelectrolytes II: synthesis and char-
acterization of poly(acrylic acid-co-alkyl acrylate). Polym Adv
Technol 2001;12:616–25.
[222] Zhang Y, Mei L, Fang Q, Zhang YX, Jiang M, Wu C. Effect
of incorporating a trace amount of fluorocarbon into poly(N-
isopropylacrylamide) on its association in water. Macromolecules
1998;31:2527–32.
[223] Zhang Y, Wu C, Fang Q, Zhang YX. A light scattering study of the
aggregation behavior of fluorocarbon modified polyacrylamides in
water. Macromolecules 1996;29:2494–7.
[224] Zhang YX, Fang Q, Fu YQ, Da AH, Zhang Y, Wu C, Hogen-Esch TE.
Synthesis and characterization of fluorocarbon-modified poly(N-
isopropylacrylamide). Polym Int 2000;49:763–74.
[225] Zhou H, Song GQ, Zhang YX, Chen JY, Jiang M, Hogen-Esch TE,
Dieing R, Ma L, Haeussling L. Hydrophobically modified poly-
electrolytes. 4. Synthesis and solution properties of fluorocarbon-
containing poly(acrylic acid). Macromol Chem Phys 2001;202:
3057–64.
[226] Armentrout RS, McCormick CL. Water soluble polymers. 76.
Electrolyte responsive cyclopolymers with sulfobetaine units
exhibiting polyelectrolyte or polyampholyte behavior in aqueous
media. Macromolecules 2000;33:419–24.
[227] Armentrout RS, McCormick CL. Water-soluble polymers. 77.
Amphoteric cyclopolymers with sulfobetaine units: phase behavior
in aqueous media and solubilization of p-cresol in microdomains.
Macromolecules 2000;33:2944–51.
[228] Chang YH, McCormick CL. Water-soluble copolymers.
57. Amphiphilic cyclocopolymers of diallylalkoxybenzyl-
methylammonium chloride and diallyl-dimethylammonium
chloride. Polymer 1994;35:3503–12.
[229] McCormick CL, Middleton JC, Cummins DF. Water-soluble copoly-
mers. 37. Synthesis and characterization of responsive hydrophobi-
cally modified polyelectrolytes. Macromolecules 1992;25:1201–6.
[230] McCormick CL, Middleton JC, Grady CE. Water soluble copolymers.
38. Synthesis and characterization of electrolyte responsive ter-
polymers of acrylamide, N-(4-butyl)phenylacrylamide, and sodium
acrylate, sodium-2-acrylamido-2-methylpropanesulphonate or
sodiu-acrylamido-3-methylbutanoate. Polymer 1992;33:4184–90.
[231] Ali SA, Umar Y, bu-Sharkh BF, Al-Muallem HA. Synthesis and com-
parative solution properties of single-, twin-, and triple-tailed
associating ionic polymers based on diallylammonium salts. J
Polym Sci Part A Polym Chem 2006;44:5480–94.
[232] Umar Y, Al-Muallem HA, bu-Sharkh BF, Ali SA. Synthesis and solu-
tion properties of hydrophobically associating ionic polymers made
from diallylammonium salts/sulfur dioxide cyclocopolymerization.
Polymer 2004;45:3651–61.
[233] Ali SA, Umar Y, Al-Muallem HA, bu-Sharkh BF. Synthesis and vis-
cosity of hydrophobically modified polymers containing dendritic
segments. J Appl Polym Sci 2008;109:1781–92.
[234] Umar Y, bu-Sharkh BF, Ali SA. The effects of charge densities
on the associative properties of a pH-responsive hydrophobi-
cally modified sulfobetaine/sulfur dioxide terpolymer. Polymer
2005;46:10709–17.
[235] Ringsdorf H, Venzmer J, Winnik FM. Fluorescence studies of
hydrophobically modified poly(N-isopropylacrylamides). Macro-
molecules 1991;24:1678–86.
[236] Wang TK, Iliopoulos I, Audebert R. Aqueous-solution behavior
of hydrophobically modified poly(acrylic acid). In: Shalaby SW,
McCormick CL, Butler GB, editors. Water soluble polymers. ACS
symposium series no. 467. Washington, DC: American Chemical
Society; 1991. p. 218–31.
[237] Xue W, Hamley IW, Castelletto V, Olmsted PD. Synthesis and
characterization of hydrophobically modified polyacrylamides
and some observations on rheological properties. Eur Polym J
2004;40:47–56.
[238] Yahaya GO, Ahdab AA, Ali SA, Abu-Sharkh BF, Hamad EZ.
Solution behavior of hydrophobically associating water-soluble
block copolymers of acrylamide and N-benzylacrylamide. Polymer
2001;42:3363–72.
[239] Reddy GJ, Naidu SV, Reddy AVR. Synthesis and characteriza-
tion of phenyl methacrylamide copolymers. Adv Polym Technol
2006;25:41–50.
[240] Zhang HP, Xu K, Ai H, Chen DH, Xv LL, Chen MC. Synthe-
sis, characterization and solution properties of hydrophobically
modified polyelectrolyte poly(AA-co-TMSPMA). J Solution Chem
2008;37:1137–48.
[241] Hwang FS, Hogen-Esch TE. Effects of water-soluble spac-
ers on the hydrophobic association of fluorocarbon-modified
poly(acrylamide). Macromolecules 1995;28:3328–35.
[242] Zhang YX, Da AH, Butler GB, Hogen-Esch TE. A fluorine-containing
hydrophobically associating polymer. 1. Synthesis and solution
properties of copolymers of acrylamide and fluorine-containing
acrylates or methacrylates. J Polym Sci Part A Polym Chem
1992;30:1383–91.
 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
[243] Bastiat G, Grassl B, Francois J. Study of sodium dodecyl sul-
fate/poly(propylene oxide) methacrylate mixed micelles for the
synthesis of thermo-associative polymers by micellar polymeriza-
tion. Polym Int 2002;51:958–65.
[244] Lara-Ceniceros AC, Rivera-Vallejo C, Jimenez-Regalado EJ. Synthesis
and characterization of telechelic polymers obtained by micellar
polymerization. Polym Bull 2007;59:499–508.
[245] Jimenez-Regalado EJ, Cadenas-Pliego G, Perez-Alvarez M,
Hernandez-Valdez Y. Study of three different families of water-
soluble copolymers: synthesis, characterization and viscoelastic
behavior of semidilute solutions of polymers prepared by solution
polymerization. Polymer 2004;45:1993–2000.
[246] McCormick CL, Hoyle CE, Clark MD. Water-soluble copolymers.
36. Photphysical investigations of water-soluble copolymers
of 2-(1-naphthylacetamide)ethylacrylamide. Macromolecules
1991;24:2397–403.
[247] McCormick CL, Hoyle CE, Clark MD. Water-soluble copolymers.
35. Photophysical and rheological studies of the copolymer of
methacrylic acid with 2-(1-naphthylacetyl)ethyl acrylate. Macro-
molecules 1990;23:3124–9.
[248] Emmons WD, Stevens TE. Acrylamide copolymer thickener for
aqueous systems. US Pat 4,395,524; 1983.
[249] Emmons WD, Stevens TE. Acrylamid-copolymers suitable as thick-
ening agent for aqueous systems and aqueous compositions
containing them. Eur Pat 63018; 1982.
[250] Kulicke W-M, Kniewske R, Klein J. Preparation, characterization,
solution properties and rheological behaviour of polyacrylamide.
Prog Polym Sci 1982;8:373–468.
[251] Evani S. Water-dispersible hydrophobic thickening agent. Eur Pat
57875; 1982.
[252] Evani S. Water-dispersible hydrophobic thickening agent. US Pat
4,432,881; 1984.
[253] Bock J, Siano DB, Kowalik RM, Turner SP. Process for forming
acrylamide-alkyl acrylamide copolymers. Eur Pat 115213; 1984.
[254] Turner SP, Siano DB, Bock J. Acrylamide–alkylacrylamide copoly-
mers. US Pat 4,520,182; 1985.
[255] Turner SP, Siano DB, Bock J. Microemulsion process for producing
acrylamide-alkyl acrylamide copolymers. US Pat 4,521,580;1985.
[256] Turner SP, Siano DB, Bock J. Micellar process for the production of
acrylamide-alkyl acrylamide copolymers. US Pat 4,528,348;1985.
[257] Vittadello ST, Biggs S. Shear history effects in associative thickener
solutions. Macromolecules 1998;31:7691–7.
[258] Regalado EJ, Selb J, Candau F. Viscoelastic behavior of semidi-
lute solutions of multisticker polymer chains. Macromolecules
1999;32:8580–8.
[259] Shashkina YA, Zaroslov YD, Smirnov VA, Philippova OE, Khokhlov
AR, Pryakhina TA, Churochkina NA. Hydrophobic aggregation in
aqueous solutions of hydrophobically modified polyacrylamide in
the vicinity of overlap concentration. Polymer 2003;44:2289–93.
[260] Ma J-T, Huang R-H, Zhao L, Zhang X. Solution properties of
ionic hydrophobically associating polyacrylamide with an arylalkyl
group. J Appl Polym Sci 2005;97:316–21.
[261] Bock J, Valint PL. Process for preparing hydrophobically associating
terpolymers containing sulfonate functionality. US Pat 4,730,028;
1988.
[262] Valint PL, Bock J. Hydrophobically associating terpolymers contain-
ing sulfonate functionality. US Pat 5,089,578; 1992.
[263] Bock J, Siano DB, Turner SP. Hydrophobically associating terpoly-
mers of acrylamide, salts of acrylic acid and alkyl acrylamide. US
Pat 4,694,046; 1987.
[264] Schulz DN, Berluche E, Maurer JJ, Bock J. Tetrapolymers of N-vinyl
pyrrolidone/acrylamide/salt of acrylic acid/N-alkyl acrylamide. US
Pat 4,663,408; 1987.
[265] Hill A, Candau F, Selb J. Aqueous solution properties of hydrophobi-
cally associating copolymers. Prog Colloid Polym Sci 1992;84:61–5.
[266] Camail M, Margaillan A, Martin I. Copolymers of N-alkyl- and N-
arylalkylacrylamides with acrylamide: influence of hydrophobic
structure on associative properties. Part 1. Viscometric behaviour
in dilute solution and drag reduction performance. Polym Int
2009;58:149–54.
[267] Camail M, Margaillan A, Martin I. Copolymers of N-alkyl- and N-
arylalkylacrylamides with acrylamide: influence of hydrophobic
structure on associative properties. Part 2. Rheological behaviour
in semi-dilute solution. Polym Int 2009;58:155–62.
[268] Zhao Y, Zhou J, Xu X, Liu W, Zhang J, Fan M, Wang J. Synthesis
and characterization of a series of modified polyacrylamide. Colloid
Polym Sci 2009;287:237–41.
[269] Seery TAP, Yassini M, Hogen-Esch TE, Amis EJ. Static and dynamic
light scattering characterization of solutions of hydrophobically
1625
associating fluorocarbon-containing polymers. Macromolecules
1992;25:4784–91.
[270] Zhang YX, Da AH, Hogen-Esch TE. A fluorocarbon-containing
hydrophobically associating polymer. J Polym Sci Part C Polym Lett
1990;28:213–8.
[271] Amis EJ, Hu N, Seery TAP, Hogen-Esch TE, Hwang F. Associating
polymers containing fluorocarbon hydrophobic units. In: Glass JE,
editor. Hydrophilic polymers—performance with environmental
acceptance. Advances in chemistry series 248. Washington, DC:
American Chemical Society; 1996. p. 279–302.
[272] Umar Y, Abu-Sharkh BF, Ali SA. The effects of zwitterionic and
anionic charge densities in polymer chains on the viscosity
behavior of a pH-responsive hydrophobically modified ionic poly-
mer. J Appl Polym Sci 2005;98:1404–11.
[273] Fevola MJ, Bridges JK, Kellum MG, Hester RD, McCormick
CL. pH-responsive polyzwitterions: a comparative study of
acrylamide-based polyampholyte terpolymers and polybetaine
copolymers. J Appl Polym Sci 2004;94:24–39.
[274] Johnson KM, Poe GD, Lockhead RY, McCormick CL. The synthe-
sis of hydrophobically modified water-soluble polyzwitterionic
copolymers and responsiveness to surfactants in aqueous solution.
J Macromol Sci Part A Pure Appl Chem 2004;41:587–611.
[275] Candau F, Biggs S, Hill A, Selb J. Synthesis, structure and prop-
erties of hydrophobically associating polymers. Prog Org Coat
1994;24:11–9.
[276] Branham KD, Middleton JC, McCormick CL. Photophysical and rhe-
ological properties of naphthalene-labeled water-soluble copoly-
mers polymerized in surfactant solution. Polym Prepr Am Chem
Soc 1991;32(1):106.
[277] Candau F, Volpert E, Lacik I, Selb J. Free-radical polymerization
in micellar media: effect of microenvironment. Macromol Symp
1996;111:85–94.
[278] Wang G-J, Engberts JBFN. Synthesis of hydrophobically and elec-
trostatically modified polyacrylamides and their catalytic effects
on the unimolecular decarboxylation of 6-nitrobenzisoxazole-3-
carboxylate anion. Langmuir 1995;11:3856–61.
[279] Vaskova V, Renoux D, Bernard M, Selb J, Candau F. Mechanism of
copolymerization of acrylamide with a polymerizable surfactant.
Polym Adv Technol 1995;6:441–51.
[280] Renoux D, Selb J, Candau F. Aqueous solution properties of
hydrophobically associating copolymers. Prog Colloid Polym Sci
1994;97:213–7.
[281] Charalambopoulou A, Bokias G, Staikos G. Template copolymerisa-
tion of N-isopropylacrylamide with a cationic monomer: influence
of the template on the solution properties of the product. Polymer
2002;43:2637–43.
[282] Rainaldi I, Cristallini C, Ciardelli G, Giusti P. Copolymerization
of acrylic acid and 2-hydroxyethyl methacrylate onto poly(N-
vinylpyrrolidone): template influence on comonomer reactivity.
Macromol Chem Phys 2000;201:2424–31.
[283] Frisch HL, Xu QH. Copolymerization of styrene and methacrylic-
acid in the presence of poly(2-vinylpyridine) as the template.
Macromolecules 1992;25:5145–9.
[284] Jantas R, Polowinski S. Copolymerization of a multiallyl monomer
with styrene. Acta Polym 1989;40:225–8.
[285] Polowinski S, Janowska G. Thermal copolymerization of acryloni-
trile with methacrylate units arranged in matrix. Eur Polym J
1975;11:183–5.
[286] Effing JJ, McLennan IJ, Kwak JCT. Associative phase separation
observed in a hydrophobically modified poly(acrylamide)/sodium
dodecyl sulfate system. J Phys Chem 1994;98:2499–502.
[287] Effing JJ, McLennan IJ, van Os NM, Kwak JCT. 1 H NMR
investigations of the interactions between anionic surfactants
and hydrophobically modified poly(acrylamide)s. J Phys Chem
1994;98:12397–402.
[288] McCormick CL, Salazar LC. Water-soluble copolymers. 45.
Ampholytic terpolymers of acrylamide with sodium 3-
acrylamido-3-methylbutanoate and 2-acrylamido-2-methyl-
propanetrimethylammonium chloride. J Appl Polym Sci
1993;48:1115–20.
[289] Peiffer DG, Lundberg RD. Synthesis and viscometric prop-
erties of low charge-density ampholytic ionomers. Polymer
1985;26:1058–68.
[290] Petit-Agnely F, Iliopoulos I, Zana R. Hydrophobically modified
sodium polyacrylates in aqueous solutions: association mechanism
and characterization of the aggregates by fluorescence probing.
Langmuir 2000;16:9921–7.
[291] Leibler L, Rubinstein M, Colby RH. Dynamics of reversible networks.
Macromolecules 1991;24:4701–7.
1626 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
[292] Candau F, Regalado EJ, Selb J. Scaling behavior of the zero shear
viscosity of hydrophobically modified poly(acrylamide)s. Macro-
molecules 1998;31:5550–2.
[293] Feng Y, Billon L, Grassl B, Bastiat G, Borisov O, François J.
Hydrophobically associating polyacrylamides and their partially
hydrolyzed derivatives prepared by post modification. 2. Proper-
ties of non-hydrolyzed polymers in pure water and brine. Polymer
2005;46:9283–95.
[294] Feng Y, Grassl B, Billon L, Khoukh A, Francois J. Effects of
NaCl on steady rheological behaviour in aqueous solutions
of hydrophobically modified polyacrylamide and its partially
hydrolyzed analogues prepared by post modification. Polym Int
2002;51:939–47.
[295] Witten Jr TA, Cohen MH. Cross-linking in shear-thickening
ionomers. Macromolecules 1985;18:1915–8.
[296] Ballard MJ, Buscall R, Waite FA. The theory of shear-thickening
polymer solutions. Polymer 1988;29:1287–93.
[297] Maerker JM, Sinton SW. Rheology resulting from shear-induced
structure in associating polymer-solutions. J Rheol 1986;30:77–99.
[298] Berret JF, Calvet D, Collet A, Viguier M. Fluorocarbon associative
polymers. Curr Opin Colloid Interface Sci 2003;8:296–306.
[299] Kujawa P, udibert-Hayet A, Selb J, Candau F. Rheological properties
of multisticker associative polyelectrolytes in semidilute aqueous
solutions. J Polym Sci Part B Polym Phys 2004;42:1640–55.
[300] Magny B, Iliopoulos I, Zana R, Audebert R. Mixed micelles formed
by cationic surfactants and anionic hydrophobically modified poly-
electrolytes. Langmuir 1994;10:3180–7.
[301] Iliopoulos I, Olsson U. Polyelectrolyte association to micelles and
bilayers. J Phys Chem 1994;98:1500–5.
[302] Chang Y, Lochhead RY, McCormick CL. Water-soluble copolymers.
50. Effect of surfactant addition on the solution properties of
amphiphilic copolymers of acrylamide and dimethyldodecyl(2-
acrylamidoethyl)ammonium bromide. Macromolecules
1994;27:2145–50.
[303] Winnik FM, Ringsdorf H, Venzmer J. Interactions of surfactants with
hydrophobically modified poly(N-isopropylacrylamides). 1. Fluo-
rescence probe studies. Langmuir 1991;7:905–11.
[304] Winnik FM, Ringsdorf H, Venzmer J. Interaction of surfactants with
hydrophobically modified poly(N-isopropylacrylamides). 2. Fluo-
rescence label studies. Langmuir 1991;7:912–7.
[305] Penott-Chang EK, Gouveia L, Fernandez IJ, Muller AJ, az-Barrios A,
Saez A. Rheology of aqueous solutions of hydrophobically modified
polyacrylamides and surfactants. Colloids Surf A 2007;295:99–106.
[306] Gouveia LM, Muller AJ. The effect of NaCl addition on the rheo-
logical behavior of cetyltrimethylammonium p-toluenesulfonate
(CTAT) aqueous solutions and their mixtures with hydropho-
bically modified polyacrylamide aqueous solutions. Rheol Acta
2009;48:163–75.
[307] Nyström B, Thuresson K, Lindman B. Rheological and dynamic
light-scattering studies on aqueous solutions of a hydrophobically
modified nonionic cellulose ether and its unmodified analogue.
Langmuir 1995;11:1994–2002.
[308] Goddard ED, Leung PS. Studies of gel formation, phase behavior and
surface tension in mixtures of a hydrophobically modified cationic
cellulose polymer and surfactant. Colloids Surf 1992;65:211–9.
[309] Goddard ED, Leung PS. Interaction of cationic surfactants with
a hydrophobically modified cationic cellulose polymer. Langmuir
1992;8:1499–500.
[310] L’Alloret F, Hourdet D, Audebert R. Aqueous solution behav-
ior of new thermoassociative polymers. Colloid Polym Sci
1995;273:1163–73.
[311] Taylor LD, Cerankowski LD. Preparation of films exhibiting a
balanced temperature-dependence to permeation by aqueous-
solutions—study of lower consolute behavior. J Polym Sci Part A
Polym Chem 1975;13:2551–70.
[312] Guillet JE, Rendall WA. Studies of the antenna effect in polymer-
molecules. 8. Photophysics of water-soluble copolymers of
1-naphthylmethyl methacrylate and acrylic-acid. Macromolecules
1986;19:224–30.
[313] Jenkins RD. The fundamental thickening mechanism of associative
polymers in latex systems, a rheological study. PhD Dissertation,
Bethlehem PA: Lehigh University; 1990.
[314] Liao D, Dai S, Tam KC. Rheological properties of hydrophobic
ethoxylated urethane (HEUR) in the presence of methylated b-
cyclodextrin. Polymer 2004;45:8339–48.
[315] Glass JE, Karunasena A. Associative thickeners: from nonsense to
reality. Polym Mater Sci Eng 1989;61:145–52.
[316] AbrahmsenAlami S, Alami E, Francois J. The lyotropic cubic phase of
model associative polymers: small-angle X-ray scattering (SAXS),
differential scanning calorimetry (DSC), and turbidity measure-
ments. J Colloid Interface Sci 1996;179:20–33.
[317] Emmons WD, Valley H, Stevens TE. Polyurethane thickeners in latex
compositions. US Pat 4,079,028; 1978.
[318] Xu B, Yekta A, Li L, Masoumi Z, Winnik MA. The functional-
ity of associative polymer networks: the association behavior of
hydrophobically modified urethane-ethoxylate (HEUR) associative
polymers in aqueous solution. Colloids Surf A 1996;112:239–50.
[319] Yekta A, Xu B, Duhamel J, Adiwidjaja H, Winnik MA. Fluorescence
studies of associating polymers in water: determination of the
chain end aggregation number and a model for the association
process. Macromolecules 1995;28:956–66.
[320] Kaczmarski JP, Glass JE. Synthesis and characterization of step-
growth hydrophobically-modified ethoxylated urethane associa-
tive thickeners. Langmuir 1994;10:3035–42.
[321] Liu F, Frere Y, Francois J. Association properties of poly(ethylene
oxide) modified by pendant aliphatic groups. Polymer
2001;42:2969–83.
[322] Barmar M, Barikani M, Kaffashi B. Synthesis of ethoxylated ure-
thane and modification with cetyl alcohol as thickener. Iran Polym
J 2001;10:331–5.
[323] Barmar M. Study of the effect of PEG length in uni-HEUR thickener
behavior. J Appl Polym Sci 2009;111:1751–4.
[324] Barmar M, Barikani M, Kaffashi B. Steady shear viscosity study of
various HEUR models with different hydrophilic and hydrophobic
sizes. Colloids Surf A 2005;253:77–82.
[325] Barmar M, Barikani M, Kaffashi B. The effect of molecular weight
on the behaviour of step-growth hydrophobically modified ethoxy-
lated urethane (S-G HEUR) end-capped with dodecyl alcohol. Iran
Polym J 2004;13:241–6.
[326] Vorobyova O, Yekta A, Winnik MA, Lau W. Fluorescent probe studies
of the association in an aqueous solution of a hydrophobically mod-
ified poly(ethylene oxide). Macromolecules 1998;31:8998–9007.
[327] Wang YC, Winnik MA. Onset of aggregation for water-soluble
polymeric associative thickeners—a fluorescence study. Langmuir
1990;6:1437–9.
[328] Fonnum G, Bakke J, Hansen FK. Associative thickeners. Part 1.
Synthesis, rheology and aggregation behavior. Colloid Polym Sci
1993;271:380–9.
[329] Xu B, Li L, Yekta A, Masoumi Z, Kanagalingam S, Winnik MA, Zhang
K, MacDonald PM, Menchen S. Synthesis, characterization, and
rheological behavior of polyethylene glycols end-capped with flu-
orocarbon hydrophobes. Langmuir 1997;13:2447–56.
[330] Calvet D, Collet A, Viguier M, Berret J-F, Séréro Y. Perfluoroalkyl
end-capped poly(ethylene oxide). Synthesis, characterization,
and rheological behavior in aqueous solution. Macromolecules
2003;36:449–57.
[331] Séréro Y, Aznar R, Porte G, Berret J-F, Calvet D, Collet A, Viguier M.
Associating polymers: from “Flowers” to transient networks. Phys
Rev Lett 1998;82:5584–7.
[332] Hartmann P, Collet A, Viguier M. Synthesis and characterization
of model fluoroacylated poly(ethylene oxide). J Fluorine Chem
1999;95:145–51.
[333] Zhang HS, Hogen-Esch TE, Boschet F, Margaillan A. Complex
formation of beta-cyclodextrin- and perfluorocarbon-modified
water-soluble polymers. Langmuir 1998;14:4972–7.
[334] Boschet F, Branger C, Margaillan A, Condamine E. Synthesis, charac-
terisation and aqueous behaviour of a one-ended perfluorocarbon-
modified poly(ethylene glycol). Polymer 2002;43:5329–34.
[335] Hu YZ, Zhao CL, Winnik MA, Sundararajan PR. Fluorescence studies
of the interaction of sodium dodecyl-sulfate with hydrophobically
modified poly(ethylene oxide). Langmuir 1990;6:880–3.
[336] Wetzel WH, Chen M, Glass JE. Associative thickeners. An overview
with an emphasis on synthetic procedures. In: Glass JE, editor.
Hydrophilic polymers—performance with environmental accep-
tance. Advances in chemistry series 248. Washington, DC:
American Chemical Society; 1996. p. 163–79.
[337] Yekta A, Nivaggioli T, Kanagalingam S, Xu B, Masoumi Z, Winnik
MA. Urethane-coupled poly(ethylene glycol) polymers containing
hydrophobic end groups: NMR characterization as a step toward
determining aggregation numbers in aqueous solutions. In: Glass
JE, editor. Hydrophilic polymers—performance with environmen-
tal acceptance. Advances in chemistry series 248. Washington, DC:
American Chemical Society; 1996. p. 363–76.
[338] Yekta A, Duhamel J, Adiwidjaja H, Brochard P, Winnik MA. Asso-
ciation structure of telechelic associative thickeners in water.
Langmuir 1993;9:881–3.
[339] Singer W, Tenneck NJ, Driscoll AE. Method of improving viscosity
stability of aqueous compositions. US Pat 3,770,684; 1973.
 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
[340] Daoud M, Cotton JP. Star shaped polymers, a model for the confor-
mation and its concentration dependence. J Phys 1983;43:531–8.
[341] Witten TA, Pincus PA. Colloid stabilization by long grafted poly-
mers. Macromolecules 1986;19:2509–13.
[342] Semenov AN, Joanny J-F, Khokhlov AR. Associating poly-
mers: equilibrium and linear viscoelasticity. Macromolecules
1995;28:1066–75.
[343] Xu B, Yekta A, Winnik MA, Sadeghy-Dalivand K, James DF, Jenkins R,
Basset D. Viscoelastic properties in water of comb associative poly-
mers based on poly(ethylene oxide). Langmuir 1997;13:6903–11.
[344] Alami E, AbrahmsenAlami S, Vasilescu M, Almgren M. A comparison
between hydrophobically end-gapped poly(ethylene oxide) with
ether and urethane bonds. J Colloid Interface Sci 1997;193:152–62.
[345] Tanaka F, Edwards SF. Viscoelastic properties of physically
crosslinked networks. Part 1. Non-linear stationary viscoelasticity.
J Non-Newtonian Fluid Mech 1992;43:247–71.
[346] Tanaka F, Edwards SF. Viscoelastic properties of physically
crosslinked networks. Part 2. Dynamic mechanical moduli. J Non-
Newtonian Fluid Mech 1992;43:273–88.
[347] Tanaka F, Edwards SF. Viscoelastic properties of physically
crosslinked networks. Part 3. Time-dependent phenomena. J Non-
Newtonian Fluid Mech 1992;43:289–309.
[348] Tanaka F, Edwards SF. Viscoelastic properties of physically cross-
linked networks. Transient network theory. Macromolecules
1992;25:1516–23.
[349] Groot RD, Agterof WGM. Dynamic viscoelastic modulus of
associative polymer networks: off-lattice simulations, theory
and comparison to experiments. Macromolecules 1995;28:
6284–95.
[350] Annable T, Buscall R, Ettelaie R. Network formation and its con-
sequences for the physical behaviour of associating polymers in
solution. Colloids Surf A 1996;112:97–116.
[351] Milner ST, Witten TA. Bridging attraction by telechelic polymers.
Macromolecules 1992;25:5495–503.
[352] Witten TA. Associating polymers and shear thickening. J Phys
1988;49:1055–63.
[353] Annable T, Buscall R, Ettelaie R, Shepherd P, Whittlestone D. Influ-
ence of surfactants on the rheology of associating polymers in
solution. Langmuir 1994;10:1060–70.
[354] Zhang K, Xu B, Winnik MA, MacDonald PM. Surfactant interactions
with HEUR associating polymers. J Phys Chem 1996;100:9834–41.
[355] Binana-Limbele W, Clouet F, Francois J. Hydrophobically end-
capped poly(ethylene oxide) urethanes. Part 3. Effect of sodium
dodecyl sulfate on their association in aqueous solution. Colloid
Polym Sci 1993;271:748–58.
[356] Persson K, Wang G, Olofsson G. Self-diffusion, thermal effects and
viscosity of a monodisperse associative polymer. Self-association
and interaction with surfactants. J Chem Soc Faraday Trans
1994;90:3555–62.
[357] Persson K, Bales BL. EPR study of an associative polymer in solu-
tion. Determination of aggregation number and interactions with
surfactants. J Chem Soc Faraday Trans 1995;91:2863–70.
[358] Kim D-H, Kom J-W, Oh S-G, Kim J, Han S-H, Chung DJ, Suh
K-D. Effects of nonionic surfactant on the rheological prop-
erty of associative polymers in complex formulations. Polymer
2007;48:3817–21.
[359] Lundberg DJ, Ma Z, Alahapperuna K, Glass JE. Surfactant influences
on hydrophobically modified thickener rheology. In: Schulz DN,
Glass JE, editors. Polymers as rheology modifiers. ACS symposium
series no. 462. Washington, DC: American Chemical Society; 1991.
p. 234–53.
[360] Harada A. Design and construction of supramolecular architec-
tures consisting of cyclodextrins and polymers. Metal complex
catalysts supercritical fluid polymerization supramolecular archi-
tecture. Adv Polym Sci 1997;133:141–91.
[361] Liao D, Dai S, Tam KC. Rheological properties of a telechelic associa-
tive polymer in the presence of a- and methylated b-cyclodextrins.
J Phys Chem 2007;111:371–8.
[362] Liao D, Dai S, Tam KC. Interaction between fluorocarbon end-
capped poly(ethylene oxide) and cyclodextrins. Macromolecules
2007;40:2936–45.
[363] English RJ, Raghavan SR, Jenkins RD, Khan SA. Associative polymers
bearing n-alkyl hydrophobes: rheological evidence for micro-gel
behavior. J Rheol 1999;43:1175–94.
[364] Jenkins RD, DeLong LM, Bassett DR. Influence of alkali-soluble asso-
ciative emulsion polymer architecture on rheology. In: Glass JE,
editor. Hydrophilic polymers—performance with environmental
acceptance. Advances in chemistry series 248. Washington, DC:
American Chemical Society; 1996. p. 425–47.
1627
[365] Prazeres TJV, Duhamel J, Olesen K, Shay G. Correlations between
the viscoelastic behavior of pyrene-labeled associative polymers
and the associations of their fluorescent hydrophobes. J Phys Chem
B 2005;109:17406–16.
[366] Tirtaatmadja V, Tam KC, Jenkins RD. Superposition of oscillations
on steady share flow as a technique for investigating the structure
of associative polymers. Macromolecules 1997;30:1426–33.
[367] Tirtaatmadja V, Tam KC, Jenkins RD. Rheological properties of
model alkali-soluble associative (HASE) polymers: effect of varying
hydrophobe chain length. Macromolecules 1997;30:3271–82.
[368] Tam KC, Guo L, Jenkins RD, Bassett DR. Viscoelastic properties of
hydrophobically modified alkali-soluble emulsion in salt solutions.
Polymer 1999;40:6369–79.
[369] Dai S, Tam KC, Jenkins RD. Microstructure of dilute hydrophobically
modified alkali soluble emulsion in aqueous salt solution. Macro-
molecules 2000;33:404–11.
[370] Nagashima K, Strashko V, MacDonald PM, Jenkins RD, Bassett DR.
Diffusion of model hydrophobic alkali-swellable emulsion associa-
tive thickeners. Macromolecules 2000;33:9329–39.
[371] English RJ, Gulati HS, Jenkins RD, Khan SA. Solution rheology of
a hydrophobically modified alkali-soluble associative polymer. J
Rheol 1997;41:427–44.
[372] Jenkins RD, Bassett DR, Shay GD. Polymers containing
macromonomers. US Pat 5,292,843; 1994.
[373] Siu H, Duhamel J. Comparison of the association level of a pyrene-
labeled associative polymer obtained from an analysis based on
two different models. J Phys Chem B 2005;109:1770–80.
[374] Prazeres TJV, Beingessner R, Duhamel J, Olesen K, Shay G, Bas-
sett DR. Characterization of the association level of pyrene-labeled
HASEs by fluorescence. Macromolecules 2001;34:7876–84.
[375] Siu H, Duhamel J. Associations between a pyrene-labeled
hydrophobically modified alkali swellable emulsion copolymer and
sodium dodecyl sulfate probed by fluorescence, surface tension,
and viscometry. Macromolecules 2006;39:1144–55.
[376] Wu W, Shay GD. Tailoring HASE rheology through polymer design:
effects of hydrophobe size, acid content, and molecular weight. J
Coat Technol Res 2005;2:423–33.
[377] Siddiq M, Tam KC, Jenkins RD. Dissolution behaviour of model
alkali-soluble emulsion polymers: effects of molecular weights and
ionic strength. Colloid Polym Sci 1999;277:1172–8.
[378] Knaebel A, Skouri R, Munch JP, Candau SJ. Structural and rheologi-
cal properties of hydrophobically modified alkali-soluble emulsion
solutions. J Polym Sci Part B Polym Phys 2002;40:1985–94.
[379] Tan H, Tam KC, Jenkins RD. Network structure of a model HASE
polymer in semidilute salt solutions. J Appl Polym Sci 2001;79:
1486–96.
[380] Tam KC, Farmer ML, Jenkins RD, Bassett DR. Rheological proper-
ties of hydrophobically modified alkali-soluble polymers—effects
of ethylene-oxide chain length. J Polym Sci Part B Polym Phys
1998;36:2275–90.
[381] Ng WK, Tam KC, Jenkins RD. Rheological properties of methacrylic
acid/ethyl acrylate co-polymer: comparison between an
unmodified and hydrophobically modified system. Polymer
2001;42:249–59.
[382] Seng WP, Tam KC, Jenkins RD. Rheological properties of model
alkali-soluble associative (HASE) polymer in ionic and non-ionic
surfactant solutions. Colloids Surf A 1999;154:365–82.
[383] Tirtaatmadja V, Tam KC, Jenkins RD. Effects of temperature on the
flow dynamics of a model HASE associative polymer in nonionic
surfactant solutions. Langmuir 1999;15:7537–45.
[384] Tirtaatmadja V, Tam KC, Jenkins RD. Effect of a nonionic surfactant
on the flow dynamics of a model HASE associative polymer. AIChE
J 1998;44:2756–65.
[385] Aubry T, Moan M. Influence of a nonionic surfactant on the rheol-
ogy of a hydrophobically associating water soluble polymer. J Rheol
1996;40:441–8.
[386] Kjoniksen AL, Beheshti N, Kotlar HK, Zhu KZ, Nystrom B. Modified
polysaccharides for use in enhanced oil recovery applications. Eur
Polym J 2008;44:959–67.
[387] Kawakami K, Ihara T, Nishioka T, Kitsuki T, Suzuki Y. Salt toler-
ance of an aqueous solution of a novel amphiphilic polysaccharide
derivative. Langmuir 2006;22:3337–43.
[388] Ihara T, Nishioka T, Kamitani H, Kitsuki T. Solution properties of a
novel polysaccharide derivative. Chem Lett 2004;33:1094–5.
[389] Akiyama E, Yamamoto T, Yago Y, Hotta H, Ihara T, Kitsuki T. Thicken-
ing properties and emulsification mechanisms of new derivatives
of polysaccharide in aqueous solution. 2. The effect of the substitu-
tion ratio of hydrophobic/hydrophilic moieties. J Colloid Interface
Sci 2007;311:438–46.
1628 D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 1558–1628
[390] Karlberg M, Thuresson K, Piculell L, Lindman B. Mixed solutions of
hydrophobically modified graft and block copolymers. Colloids Surf
A 2004;236:159–64.
[391] Hwang FS, Hogenesch TE. Fluorocarbon-modified water-soluble
cellulose derivatives. Macromolecules 1993;26:3156–60.
[392] Dai SS, Ye L, Huang RH. A study on the solution behavior of IPBC-
hydrophobically-modified hydroxyethyl cellulose. J Appl Polym Sci
2006;100:2824–31.
[393] Ye L, Li Q, Huang RH. Study on the rheological behavior of
the hydrophobically modified hydroxyethyl cellulose with 1,2-
epoxyhexadecane. J Appl Polym Sci 2006;101:2953–9.
[394] Li Q, Ye L, Cai Y, Huang RH. Study of rheological behavior of
hydrophobically modified hydroxyethyl cellulose. J Appl Polym Sci
2006;100:3346–52.
[395] Gonzalez JM, Muller AJ, Torres MF, Saez AE. The role of shear
and elongation in the flow of solutions of semi-flexible polymers
through porous media. Rheol Acta 2005;44:396–405.
[396] Shaw KG, Leipold DP. New cellulosic polymers for rheology control
of latex paints. J Coat Technol 1985;57:63–72.
[397] Kästner U, Hoffmann H, Donges R, Ehrler R. Interactions between
modified hydroxyethyl cellulose (HEC) and surfactants. Colloids
Surf A 1996;112:209–25.
[398] Stone FW, Rutherford JM Jr. Quaternary nitrogen-containing cellu-
lose ethers. US Pat 3,472,840; 1969.
[399] Kästner U, Hoffmann H, Donges R, Ehrler R. Hydrophobically and
cationically modified hydroxyethyl cellulose and their interactions
with surfactants. Colloids Surf A 1994;82:279–97.
[400] Winnik FM, Winnik MA, Tazuke S, Ober CK. Synthesis and char-
acterization of pyrene-labeled (hydroxypropyl)cellulose and its
fluorescence in solution. Macromolecules 1987;20:38–44.
[401] Karlson L, Joabsson F, Thuresson K. Phase behavior and rheology
in water and in model paint formulations thickened with HM-
EHEC: influence of the chemical structure and the distribution of
hydrophobic tails. Carbohydr Polym 2000;41:25–35.
[402] Badiger MV, Lutz A, Wolf BA. Interrelation between the ther-
modynamic and viscometric behaviour of aqueous solutions of
hydrophobically modified ethyl hydroxyethyl cellulose. Polymer
2000;41:1377–84.
[403] Um SU, Poptoshev E, Pugh RJ. Aqueous solutions of ethyl (hydrox-
yethyl) cellulose and hydrophobic modified ethyl (hydroxyethyl)
cellulose polymer: dynamic surface tension measurements. J Col-
loid Interface Sci 1997;193:41–9.
[404] Zou S, Zhang WK, Zhang X, Jiang BZ. Study on polymer micelles
of hydrophobically modified ethyl hydroxyethyl cellulose using
single-molecule force spectroscopy. Langmuir 2001;17:4799–808.
[405] Nishikawa K, Yekta A, Pham HH, Winnik MA, Sau AC. Fluores-
cence studies of hydrophobically modified hydroxyethylcellulose
(HMHEC) and pyrene labeled HMHEC. Langmuir 1998;14:7119–29.
[406] Miyajima T, Kitsuki T, Kita K, Kamitani H, Yamaki K. Polysaccha-
ride derivative, and preparation process and use thereof. US Pat
5,891,450; 1999.
[407] Boström P, Ingvarsson I, Sundberg K. Water soluble nonionic cellu-
lose ethers and their use in paints. US Pat 5,140,099; 1992.
[408] Tanaka R, Meadows J, Phillips GO, Williams PA. Viscometric and
spectroscopic studies on the solution behavior of hydrophobically
modified cellulosic polymers. Carbohydr Polym 1990;12:443–59.
[409] Landoll LM. Modified nonionic cellulose ethers. US Pat 4,228,277;
1980.
[410] Zhao GQ, Chen SB. Nonlinear rheology of aqueous solutions of
hydrophobically modified hydroxyethyl cellulose with nonionic
surfactant. J Colloid Interface Sci 2007;316:858–66.
[411] Maestro A, Gonzalez C, Gutierrez JM. Thickening mechanism in
associative polymers. Macromol Symp 2002;187:919–27.
[412] Picton L, Muller G. Rheological properties of modified cellulosic
polymers in semi-dilute regime: effect of salinity and temperature.
Prog Colloid Polym Sci 1996;102:26–31.
[413] Maestro A, Gonzalez C, Gutierrez JM. Shear thinning and thixotropy
of HMHEC and HEC water solutions. J Rheol 2002;46:1445–57.
[414] Winnik FM. Effect of temperature on aqueous-solutions of
pyrene-labeled (hydroxypropyl)cellulose. Macromolecules
1987;20:2745–50.
[415] Zhao GQ, Khin CC, Chen SB, Chen BH. Nonionic surfactant
and temperature effects on the viscosity of hydrophobically
modified hydroxyethyl cellulose solutions. J Phys Chem B
2005;109:14198–204.
[416] Dualeh AJ, Steiner CA. Hydrophobic microphase formation in
surfactant solutions containing an amphiphilic graft copolymer.
Macromolecules 1990;23:251–5.
[417] Evertsson H, Nilsson S. Microstructures formed in aqueous solu-
tions of a hydrophobically modified nonionic cellulose derivative
and sodium dodecyl sulfate: a fluorescence probe investigation.
Carbohydr Polym 1999;40:293–8.
[418] Kaczmarski JP, Tarng MR, Ma ZY, Glass JE. Surfactant and salin-
ity influences on associative thickener aqueous solution rheology.
Colloids Surf A 1999;147:39–53.
[419] Lauten RA, Nystrom B. Time dependent association phenom-
ena in dilute aqueous mixtures of a hydrophobically modified
cellulose derivative and an anionic surfactant. Colloids Surf, A
2003;219:45–53.
[420] Maestro A, Gonzalez C, Gutierrez JM. Interaction of surfactants with
thickeners used in waterborne paints: a rheological study. J Colloid
Interface Sci 2005;288:597–605.
[421] Nilsson S, Goldraich M, Lindman B, Talmon Y. Novel organized
structures in mixtures of a hydrophobically modified poly-
mer and two oppositely charged surfactants. Langmuir 2000;16:
6825–32.
[422] Nilsson S, Thuresson K, Lindman B, Nystrom B. Associations in mix-
tures of hydrophobically modified polymer and surfactant in dilute
and semidilute aqueous solutions. A rheology and PFG NMR self-
diffusion investigation. Macromolecules 2000;33:9641–9.
[423] Patruyo LG, Muller AJ, Saez AE. Shear and extensional rheology of
solutions of modified hydroxyethyl celluloses and sodium dodecyl
sulfate. Polymer 2002;43:6481–93.
[424] Piculell L, Egermayer M, Sjostrom J. Rheology of mixed solutions of
an associating polymer with a surfactant. Why are different surfac-
tants different? Langmuir 2003;19:3643–9.
[425] Thuresson K, Nystrom B, Wang G, Lindman B. Effect of surfactant on
structural and thermodynamic properties of aqueous-solutions of
hydrophobically-modified ethyl(hydroxyethyl)cellulose. Langmuir
1995;11:3730–6.
[426] Thuresson K, Soderman O, Hansson P, Wang G. Binding of SDS to
ethyl(hydroxyethyl)cellulose. Effect of hydrophobic modification
of the polymer. J Phys Chem 1996;100:4909–18.
[427] Thuresson K, Lindman B, Nystrom B. Effect of hydrophobic modi-
fication of a nonionic cellulose derivative on the interaction with
surfactants. Rheology. J Phys Chem B 1997;101:6450–9.
[428] Thuresson K, Lindman B. Effect of hydrophobic modification of
a nonionic cellulose derivative on the interaction with surfac-
tants. Phase behavior and association. J Phys Chem B 1997;101:
6460–8.
[429] Joabsson F, Rosen O, Thuresson K, Piculell L, Lindman B. Phase
behavior of a “Clouding” nonionic polymer in water. Effects of
hydrophobic modification and added surfactant on phase compo-
sitions. J Phys Chem B 1998;102:2954–9.
[430] Panmai S, Prud’homme RK, Peiffer DG, Jockusch S, Turro NJ. Interac-
tions between hydrophobically modified polymers and surfactants:
a fluorescence study. Langmuir 2002;18:3860–4.
[431] Karlberg M, Stjerndahl M, Lundberg D, Piculell L. Mixed solutions
of an associating polymer with a cleavable surfactant. Langmuir
2005;21:9756–63.
[432] Bu HT, Kjoniksen AL, Knudsen KD, Nystrom B. Effects of surfac-
tant and temperature on rheological and structural properties of
semidilute aqueous solutions of unmodified and hydrophobically
modified alginate. Langmuir 2005;21:10923–30.
[433] Nilsson S, Thuresson K, Hansson P, Lindman B. Mixed solutions
of surfactant and hydrophobically modified polymer. Controlling
viscosity with micellar size. J Phys Chem B 1998;102:7099–105.
[434] Kjoniksen AL, Nilsson S, Thuresson K, Lindman B, Nys-
trom B. Effect of surfactant on dynamic and viscoelastic
properties of aqueous solutions of hydrophobically modi-
fied ethyl(hydroxyethyl)cellulose, with and without spacer.
Macromolecules 2000;33:877–86.