Artigo Eor Polimeros

Progress in Polymer Science 36 (2011) 15581628
Contents lists available at ScienceDirect
Progress in Polymer Science

journal homepage: www.elsevier.com/locate/ppolysci
Polymers for enhanced oil recovery: A paradigm for

structureproperty relationship in aqueous solution
D.A.Z. Wever a,b,1 , F. Picchioni a,2 , A.A. Broekhuis a,
a
b
Department of Chemical Engineering - Product Technology, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands
Dutch Polymer Institute DPI, P.O. Box 902, 5600 AX Eindhoven, The Netherlands
a r t i c l e
i n f o
Article history:
Received 2 June 2010
Received in revised form 3 May 2011
Accepted 6 May 2011
Available online 27 May 2011
Keywords:
Water soluble polymers
Enhanced oil recovery (EOR)
Hydrophobically modied polymers
Polyacrylamide
Associating polymers
Solution rheology
a b s t r a c t
Recent developments in the eld of water-soluble polymers aimed at enhancing the aqueous solution viscosity are reviewed. Classic and novel associating water-soluble polymers
for enhanced oil recovery (EOR) applications are discussed along with their limitations.
Particular emphasis is placed on the structureproperty correlations and the synthetic
methods. The observed rheological properties are conceptually linked to the polymer chemical structure (1) and topology (2). In addition, the inuence of external parameters, e.g.
temperature, pH, salt, and surfactant, on the rheological behavior is reviewed. Progress
booked in deeper understanding of the structureproperty relationship is thoroughly discussed. Furthermore, a critical overview of the synthetic methods as well as of the solution
properties of these polymers is provided. In this respect the inuence of internal (i.e.
chemical structure) and external (vide supra) factors on these properties provide a conceptual 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.
2.
3.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1560
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
Recent developments in water-soluble thickening polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1566
3.1.
Hydrophobically modied polyacrylamide (HMPAM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1567
3.1.1.
Chemical structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1581
3.1.2.
3.2.
Hydrophobically modied ethoxylated urethane (HEUR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1589
3.2.1.
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) 15581628
4.
1559
3.2.3.
Effects of external parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1600
3.3.
Hydrophobically modied alkali swellable emulsion (HASE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1602
3.3.1.
3.3.2.
Effect of inherent parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1608
3.3.3.
Effect of external parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1609
3.4.
Hydrophobically modied cellulose derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1610
3.4.1.
3.4.2.
Effect of inherent parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1617
3.4.3.
Effect of external parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1617
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1619
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1619
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1619
Nomenclature
4-BA
4-butylaniline
AA
acrylic acid
ABS
alkylbenzenesulfonates
ACVA
4,4 -azobis-4-cyanopentanoic acid
AGE
alkylglycidyl ether
AM
acrylamide
AMM
associative macromonomer
AMPDAB 4-(2-acrylamido-2methylpropyldimethylammonio)
butanoate
AMPDAC 2-(acrylamido-2methylpropyldimethylammonium)
chloride
AMPDAE 2-(2-acrylamido-2methylpropyldimethylammonio)
ethanoate
AMPDAH 6-(2-acrylamido-2methylpropyldimethylammonio)
hexanoate
AMPDAPS 3-(2-acrylamido-2-methylpropanedimethylammonio)-1-propanesulfonate
AMPTAC 2-(acrylamido)-2methylpropyl]trimethylammonium
chloride
APS
N-[(1-pyrenylsulfonamido)ethyl]acrylamide
BD
bromododecane
BPAM
N-(4-butyl)phenylacrylamide
critical association concentration
CAC
C8 AM
octylacrylamide
C10 AM decylacrylamide
C12 AM dodecylacrylamide
C14 AM tetradecylacrylamide
C18 AM octadecylacrylamide
alkylacrylamide
CN AM
C12 Acl dodecyl ammonium chloride
C16 TAAc hexadecyltrimethyl ammonium acetate
C12 TABr dodecyltrimethyl ammonium bromide
C12 TACl dodecyltrimethyl ammonium chloride
C16 TACl hexadecyltrimethyl ammonium bromide
CAC
critical association concentration
CDMAO cetyldimethylamine oxide
CMC
CS*
CTA
CTAB
CTAT
critical micelle concentration

critical surfactant concentration
chain transfer agent
cetyltrimethyl ammonium bromide
cetyltrimethyl ammonium p-toluenesulfonate
Da
dalton
DAAM diacetone acrylamide
DADMAC N,N-diallyl-N,N-dimethylammonium
chloride
DADPMA [(dimethylammonioethoxy)dicyanoethenolate]propylmethacrylamide
DAGE
(3,3-dialkoxymethyl)propylglycidyl ether
DAMA N,N-diallyl-N,N-methylamine chloride
DAMAPS 3-(N,N-diallyl-Nmethylammonoi)propanesulfonate
DEmMA substituted methacrylate
DiC3 AM N,N-dipropylacrylamide
DiC6 AM N,N-dihexylacrylamide
DiC8 AM N,N-dioctylacrylamide
DiC10 AM N,N-didecylacrylamide
DiC12 AM N,N-didodecylacrylamide
DiC14 AM N,N-ditetradecylacrylamide
DiC16 AM N,N-dihexadecylacrylamide
DMSO dimethylsulfoxide
DR
drag reduction
DTAB
dodecyltrimethylammonium bromide
DTAC
dodecyltrimethylammonium chloride
EAM N-(4-ethyl-phenyl)acrylamide
EA
ethyl acrylate
EHEC
ethyl hydroxyethyl cellulose
EO
ethylene oxide
enhanced oil recovery
EOR
EP16
1,2-epoxyhexadecane
ethyl vinyl ether
EVE
FX-13
2-(N-ethylperuorosulfoamido)ethyl acrylate
2-(N-ethylperuoroFX-14
octane/sulfoamido)ethyl methacrylate
HASE
hydrophobically modied alkali swellable
emulsion
1560
H12 MDI
HDI
HEC
HEUR
bis(4-isocyanateocyclohexyl)methane
hexamethylene di-isocyanate
hydroxyethyl cellulose
hydrophobically modied ethoxylated urethane
HHM-HEC hydrophobicallyhydrophilically modied hydroxyethyl cellulose
HMPAM hydrophobically modied polyacrylamide
HM-CMC hydrophobically modied carboxymethyl
cellulose
HM-EHEC hydrophobically modied ethyl hydroxyethyl cellulose
HM-HEC hydrophobically modied hydroxyethyl
cellulose
HM-HPC hydrophobically modied hydroxypropyl
cellulose
HM-polysaccharides hydrophobically
modied
polysaccharides
HPAM partially hydrolyzed polyacrylamide
HTAC
hexadecyltrimethylammonium chloride
4-isopropylbenzyl chloride
IPBC
IPDI
isophorone diisocyanate
KDS
potassium dodecyl sulfate
lower critical solution temperature
LCST
MA
maleic anhydride
MAA
methacrylic acid
MAM
methacrylamide
MeEAM N-methyl-N-(4-ethyl-phenyl)acrylamide
MO
methyleneoxide
MWD
molecular weight distribution
sodium acrylate
NaA
NaAMB sodium 3-acrylamido-3-methylbutanoate
NaAMPS sodium 2-acrylamido-2-methylpropanesulfonate
NaC10 S sodium decyl sulfate
NaC14 S sodium tetradecyl sulfate
dodecyl-di(ethyleneoxide)NaC12 (EO)2 S sodium
sulfate
NAEA
2-(1-naphthylacetyl)ethyl acrylate
NAEAm 2-(1-naphthylacetamido)ethyl acrylamide
NaMAMB sodium 3-methacrylamido-3-methylbutanoate
NBAM N-benzylacrylamide
NIPAM N-isopropylacrylamide
NNDAM N,N-dimethyl acrylamide
nanometer
nm
NMA
[(1-naphthyl)methyl]acrylamide
nuclear magnetic resonance
NMR
NP
nonylphenol ethoxylates
NPEAM N-phenethylacrylamide
non-radiative energy transfer
NRET
OG
n-octyl -d-glucopyranoside
original oil in place
OOIP
OTG
n-octyl -d-thioglucopyranoside
poly(acrylic acid)
PAA
PAGE
poly(alkylglycidyl ether)
polyacrylamide
PAM
PDI
PEO
PGSE
PMAAM
ppm
Py
RRF
S-HEC
polydispersity index
poly(ethylene oxide)
pulse gradient spin echo
N-phenylmethacrylamide
parts per million
pyrene
residual resistance factor
hydrophilically modied hydroxyethyl cellulose
S-G HEUR step-growth hydrophobically modied
ethoxylated urethane
SANS
small-angle neutron scattering
SEC
size exclusion chromatography
SDS (NaC12 S) sodium dodecyl sulfate
SMR
surfactant to micelle ratio
SOBS
sodium octyl benzene sulfonate
THF
tetrahydrofuran
TMSPMA 3-[tris(trimethylsilyoxy)sily]propyl
methacrylate
TTAB
tetradecyltrimethyl ammonium bromide
1. Introduction
Enhanced oil recovery (EOR) is a challenging eld for
different scientic disciplines. The importance of this eld
is highlighted by the number of patents (mainly led
by multinational companies) involving polymers for EOR.
Nevertheless, the limited number of patents led in the
last 10 years (less than 25) demonstrates the difculty
of this research eld as well as the relative maturity in
the scientic and technological concepts linked to relevant applications. Given the fact that the easily recoverable
oil is running out and that much oil remains in the reservoir after conventional methods have been exhausted, the
implementation of EOR is crucial to guarantee a continuing supply. In addition, alternative energy sources have
not yet proved to be capable of meeting the world energy
demand, so that a mixture of different sources, including oil, is required to meet the world energy demand
in the near future. According to Thomas [1], approximately 7.0 1012 barrels of oil will remain in oilelds after
conventional methods have been exhausted; this value
constitutes also the target recovery for EOR. Water-soluble
polymers for EOR applications have been successfully
implemented, mainly in Chinese oilelds [2,3]. The purpose of the water-soluble polymers in this application is to
enhance the rheological properties of the displacing uid.
The oil production increases with the microscopic sweep
of the reservoir and the displacement efciency of the oil
[4]. Indeed, the use of water-soluble polymers improves
the wateroil mobility ratio [4], and leads to enhanced oil
recovery. However, given the harsh conditions present in
most oil reservoirs, new problems and limitations arise
with the use of water-soluble polymers. Besides positively
affecting solution rheology, water-soluble polymers should
withstand high salt concentration, the presence of calcium,
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 occulation [6].
New water-soluble polymers were successfully tested at
higher temperatures [7,8]. Associative water-soluble polymers were tested and showed promising results compared
to traditionally used polymers [9,10].
Several studies [1116] demonstrated that the oil is produced faster (compared to water ooding), but also more
oil can be recovered. A mechanism based on the viscoelastic properties of the polymers has been proposed to
explain the higher oil recovery. This mechanism is mainly
supported by indirect evidence and mathematical models
[1114].
Independently of the exact displacement mechanism
and efciency, the use of water-soluble polymers for EOR
still constitutes a challenging eld, 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 eld as paradigmatic for watersoluble polymers in general. Indeed, fundamental scientic
studies linked to EOR, particularly those involving the
relationship between the polymer structure and the corresponding properties in aqueous solution (e.g. viscosity),
have a conceptual character, thus providing a broad and
general understanding, valid also for other application
elds. The interaction between polymer chains in aqueous solution as well as the inuence of the solute structure
on the corresponding viscosity are of paramount importance in EOR applications, but are studied and modeled
through very general methods and theories. This general
interest in structureproperty relationships is testied by
the constantly increasing amount of scientic literature
that is dedicated to this topic [1720], the last dedicated
review (from 1990 [21]) being already outdated by the
most recent ndings. 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 scientic literature.
Section 2 presents some background information on
oil recovery methods, thus dening 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 corresponding polymer chemical structure. Subsequently,
the chemical structures are linked to the corresponding
rheological properties in water solution. The sensitivity 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 surfactant type and concentration. Relations between the
polymer structure, i.e. chemical structure and topology, are proposed for the different polymers. Finally,
in Section 4 we provide some general conclusions on
the most recent, relevant and generally accepted concepts.
1561
2. Currently used EOR polymers

2.1. Polyacrylamide (PAM)
Polyacrylamide was the rst polymer used as thickening
agent for aqueous solutions. The thickening capability (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 general framework of EOR processes, PAM is mainly used
as the reference model system for chemical modication. Many authors have reported different attempts
to alter the chemical structure of PAM or to synthesize new acrylamide-based copolymers with improved
properties, i.e. shear resistance, brine compatibility and
temperature stability [2225]. The synthesis of the copolymer N,N-dimethyl acrylamide with Na-2-acrylamido-2methylpropanesulfonate (NNDAMNaAMPS) was reported
by Sabhapondit et al. [22,23] and tested for its performance 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 NNDAMNaAMPS
copolymer [23] as compared to unmodied partially
hydrolyzed polyacrylamide, HPAM, was demonstrated.
In another example, Song et al. [24] reported the synthesis of starch-graft-poly(acrylamide-co-(2-acrylamido2-methylpropanesulfoacid)). The oil recovery rate of the
subsequent polymer solution was higher compared to
HPAM, and the novel polymer displayed better temperature and shear stability. These two examples already
dene a common research theme in the general eld
of water-soluble polymers for EOR. That is, a strategic
approach involving the chemical modication of commercial polymers (in this case PAM) to tailor and improve the
corresponding solution properties and eventually EOR performance.
2.2. Partially hydrolyzed polyacrylamide (HPAM)
HPAM, by far the most used polymer in EOR applications, is a copolymer of PAM and PAA obtained by partial
hydrolysis of PAM or by copolymerization of sodium acrylate 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
formation of the corresponding salt. According to the general theory of polyelectrolyte solutions [27], the presence of
electrostatic charges along a polymer backbone is responsible for prominent stretching (due to electric repulsion)
of the polymeric chains in water and, eventually, results
in a viscosity increase compared to the uncharged analogue. 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 signicantly different rheological behavior compared
to their neutral analogues [2931]. The thickening capability 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 polyelectrolytes are dissolved in water containing electrolytes
(salts) a reduction in viscosity is observed [26,3234]. It
has been demonstrated that the specic 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 repulsion and consequently to a less signicant 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
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 occulation [38]. It has also been demonstrated that multivalent cations can form polyionmetal
complexes which affect the viscosity of the resulting solution [3941]. 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 inuencing
the viscosity of HPAM solutions are the degree of hydrolysis, 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% experimental 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
Fig. 2. Complexation behavior of HPAM under different conditions.

Reproduced with permission from [39] 1999, ACS Publishing.
1563
Fig. 3. Schematic presentation of behavior of HPAM coils in shear ow.

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 tolerate the high mechanical forces present during the ooding
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 demonstrated 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 concentration, 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 thickening at lower shear rates [45]. By decreasing the average
molecular weight, an increase in the polymer concentration 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 polymer chains and the dissociation of entanglements between
separate polymer coils [4]. Stiffening of the polymer backbone 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-
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 formation of additional links between two chains [49]. The
shear thickening behavior is observed both in laboratory
rheometers [45] (in pure water and aqueous salt solutions) 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 conned 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 conformational change of the macromolecules is reversible
since it is commonly explained by formation at macromolecular level of reversible interactions like hydrogen
bonding. Indeed, it is believed that hydrogen bonding arises
for HPAM solutions between the carboxylic functionalities [55]. However, this is contested due to conicting
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 conrmed [57]. Hu et al. [46] proposed a
schematic presentation depicting the essential behavior of
HPAM solutions in shear ow (see Fig. 3).
Another behavior that has been identied for HPAM
solutions which is important for EOR is their negative
Fig. 4. Type I and II of rheopectic behavior of HPAM solutions.

Reproduced with permission from [58] 1995, Springer.
1564
Fig. 5. Interactions between sodium oleate and HPAM at low (A) and high (B) surfactant concentration.
thixotropic (rheopectic) property, i.e. an increase in viscosity with shear-time at a constant shear rate [32,5861].
Researchers have identied two different types of rheopectic 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 signicant impact on the
rheological properties of the subsequent solution. If the
hydrolysis degree of HPAM is too large, insolubility problems 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 inuence 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 critical 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 amplied, i.e. the effect is seen at

lower cation concentrations [61]. This is due to the higher
screening capability of multivalent cations [61]. In addition 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
inuence on the corresponding rheological behavior. Xin
et al. [63] investigated the interaction between the surfactant sodium oleate and HPAM and found that the viscosity
of the polymersurfactant aqueous solution depends on
the surfactant concentration. At low surfactant concentration 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 bonding. 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 viscosity. 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 solution, 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. waterpolymersurfactant, remains relatively
constant with further addition of SDS in the salty water. In
pure water the solution viscosity still decreases with further 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 signicant increase
is observed with further addition of SDS. The authors have
hypothesized that at low pH xation of some protons onto
the surfactant micelles occurs [64]. This changes the ionization equilibrium of the carboxylic groups leading to an
increase in the surface charge density, which corresponds
to an increase in solution viscosity.
1565
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 efcient xanthan gum producer is
the Xanthomonas campestris bacterium [65,66]. The chemical 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 2.82.02.0 [67]. The backbone 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
[6972] (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-
tions employing xanthan gum display high viscosity at

low shear rates [74] and thus the disordered conformation 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 [7780] have investigated the temperature
dependence of the apparent viscosity of xanthan gum solutions. 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 5000s1 ).
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 [8184]. Biocides are used to suppress
the growth of the xanthan gum degrading microorganisms.
In most cases formaldehyde is the most efcient biocide
Fig. 7. Conformational transition of xanthan gum.
1566
[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 combination can be benecial. According to Taugbol et al. [85]
more than 50% of the residual oil (after a waterood) can be
recovered using xanthan gum and an alkyl propoxy-ethoxy
sulfate (C1215 (PO)4 -(EO)2 -OSO3 Na+ ) as the surfactant.
The recovery of the residual oil using only a surfactant solution 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 formation of large micellar aggregates, which have a negative
effect on the ow performance of the surfactant through
the porous media.
3. Recent developments in water-soluble

thickening polymers
The limited number of available commercial polymers currently employed in EOR has been the subject
of recent developments aimed at improving their performance. Indeed, an alternative concept has been studied in
the last four decades, and involves the association between
hydrophobic groups that are incorporated in the backbone 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 modied 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 demonstrated that the addition of small amounts of surfactants
can increase the viscosity of the aqueous solution containing hydrophobically modied polymers signicantly [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 modied polyacrylamide (HMPAM) with
polyacrylamide (PAM) in a simple core ood test and
demonstrated that the residual resistance factor (RRF) after
the polymer ood is much higher for the HMPAM compared
to PAM [94]. All these modication strategies, together
with new kinds of water-soluble systems, have been extensively reported in the literature and will be discussed in the
next paragraph.
As mentioned earlier, a relatively new class of watersoluble polymers is the one constituted by hydrophobically
associative polymers [87]. The rst hydrophobically associative polymers were synthesized almost fty 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. During the 1980s when the oil crisis hit, a lot of research was
performed on EOR. From the many patents [97102] that
have been led during those years it is evident that this
accelerated the development of hydrophobically associative polymers for use in EOR applications.
Hydrophobically associative polymers contain, in
most cases, a small number of hydrophobic groups,
i.e. 818 carbon atoms moieties [103106], distributed
along the main backbone [20,107,108]. These hydrophobic groups can be distributed randomly or block-like
[88,91,103,107,109120], and coupled at one or both
ends [104,121131]. Above a given polymer concentration
(dependent on the molecular structure) the hydrophobic groups associate, when the polymer is dissolved
in water, to form hydrophobic micro-domains (intra or
intermolecular liaisons) [88,89,104,105,107,108,132135].
These lead to an increase in hydrodynamic volume, which
Fig. 8. Intra- and intermolecular associations.

in turn yields a polymer with a much better thickening

(higher viscosity [107]) capability compared to its nonassociative 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 hydrophobic groups [104,121].
The temperature dependence of the solution viscosity is an interesting property of hydrophobically modied
polymers for EOR applications. It has long been accepted
that increasing the temperature of the polymer solution
will lead to a reduction in viscosity [103,133,136140].
This since an increase in temperature implies a decrease
of the association strength of the hydrophobes. Increasing 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 temperature [141154]. Indeed, a temperature increase will
decrease the solubility of one of the components (lower
critical solution temperature [LCST]-groups) of the polymers. 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 presentation of this behavior has been presented by Hourdet
and coworkers [151] and is depicted in Fig. 9.
Above the critical overlap chain concentration this transition will lead to an increase in the viscosity of the solution
through intermolecular associations.
Fundamental research on different polymers, in binary
(polymerwater) and ternary (polymerwatersurfactant)
systems, has been performed using different techniques
which include 13 C NMR [155158] (solution or solidstate), 1 H NMR [109], 23 Na NMR [159,160], 19 F NMR
[161], NMR self-diffusion [126,162165] potentiometry [166168], static and dynamic laser light scattering [128,130,131,146,163,167172], UV-spectroscopy for
polymers bearing chromophores [88,110,111,173181],
small-angle neutron scattering (SANS) [182], non-radiative
energy transfer (NRET) studies [178,183185], size exclusion chromatography (SEC) [170,186189] and surface
tension [131,133,162,163,165].
Several different associative hydrophobically modied
polymers have been developed which include polyacrylamides (HMPAM), ethoxylated urethanes (HEUR), alkali
swellable emulsions (HASE), and polysaccharides (HMpolysaccharides). Their synthesis, rheological behavior and
adsorption on surfaces will be discussed in the following
sections.
1567
3.1. Hydrophobically modied 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 published.
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 technique as the hydrophobic monomer is not soluble in
water. In order to disperse the hydrophobic monomer,
it is dissolved using a co-solvent (homogeneous copolymerization) or a surfactant (micellar copolymerization) or
dispersed without any additives (heterogeneous copolymerization) [88,135].
Among these different methods, micellar copolymerization 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 rst reports on micellar copolymerization appeared simultaneously some 25 years ago
[251256]. A schematic presentation of this polymerization 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 completely 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 copolymerization are sodium dodecyl sulfate (SDS) [92,103,104,109,
112,121,134,135,138,173179,203,229,230,241,257260]
and cationic hexadecyltrimethylammonium bromide
(CTAB) [113,133,220,238]. Many different hydrophobic monomers have been used, such as acrylate or
methacrylate-derivatives, alkyl groups with varying number of carbons and different topologies
[99,100,103,229,261264], aryl or alkylaryl functionalities
[88,110,111,113,173177,230,260,265268], uorocarbon
containing agents [132,241,242,269271] and zwitterionic
groups [196199,201203,234,272274]. By incorporating
water-soluble spacers between the hydrophilic backbone
and the hydrophobic group an enhancement of the viscosity 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 temperature of the reaction [135]. Another parameter that has
been identied 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)

or sodium 3-acrylamido-3-methylbutanoate (NaAMB, R = 1) or
(2-acrylamido-2-methylpropyl)dimethylammonium chloride (AMPDAC, R = 3)
[190193]
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
(AMPDAPS) with 4-(2-acrylamido-2-methylpropyldimethylammonio) butanoate (AMPDAB)
[196]
Copolymer of acrylamide (AM) with

3-(2-acrylamido-2-methylpropane-dimethylammonio)-1-propanesulfonate (AMPDAPS)
[197]
Polyelectrolyte
Table 1 (Continued)
Polymer
Structure
References
Copolymer of AM with 2-(2-acrylamido-2-methylpropyldimethylammonio) ethanoate (AMPDAE,

N = 1) or AMPDAB, N = 3 or 6-(2-acrylamido-2-methylpropyldimethylammonio) hexanoate
(AMPDAH, N = 5)
[198200]
Terpolymer of AM with acrylic acid (AA) and AMPDAPS
[201]
Terpolymer of AM with sodium acrylate (NaA) and AMPDAB
[202]
Copolymer of AM with [(dimethylammonioethoxy)dicyanoethenolate]propyl-methacrylamide

(DADPMA)
[203]
1569
1570
Polyelectrolyte, zwitterionic backbone
Terpolymer of AM and AMPDAC (R1 = H) with NaAMPS (R2 = 1) or AMPTAC (R1 = CH3 ) with NaAMPS
(R2 = 1) or AMPTAC (R1 = CH3 ) with NaAMB (R2 = 2)
[204207]
[208]
Copolymer of 2-acrylamido-2-methylpropanesulfonate (NaAMPS) with

(2-acrylamido-2-methylpropyl)-dimethylammonium chloride (AMPDAC, R = H) or
[2-(acrylamido)-2-methylpropyl]trimethylammonium chloride (AMPTAC, R = CH3 )
[209211]
Polyelectrolyte, amphiphilic
Copolymer of AM (R1 = NH2 ) and sulfonate containing monomer (R2 = 1)
[115,212,213]
Terpolymer of AM with AMPDAC and sodium 3-acrylamido-3-methylbutanoate (NaAMB)
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)
[156,214216]
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)
Terpolymer of AM (R1 = NH2 ) and AA (R2 = OH) with
[175,176,217]
Copolymer of NaA and
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
Terpolymer of AA and methacrylamide (MAM) with
[185,218]
Polyelectrolyte amphiphilic
Terpolymer of maleic anhydride (MA), ethyl vinyl ether (EVE) and 4-butylaniline (4-BA)
[219]
Copolymer of AM (R1 = NH2 ) and dimethyldodecyl(2-acrylamidoethyl)ammonium bromide (DAMAB,

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)
[115,220,221]
(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
Table 1 (Continued)
Polymer
Structure
References
[221225]
Polyelectrolyte, zwitterionic monomer and amphiphilic
Copolymer of 3-(N,N-diallyl-N-methylammonio)propane-sulfonate (DAMAPS, R2 = 1) with

N,N-diallyl-N,N-dimethylammonium chloride (DADMAC, R1 = CH3 ) or N,N-diallyl-N-methylamine
chloride (DAMA, R1 = H)
[226228]
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)
Copolymers of N-isopropylacrylamide (NIPAM, R2 = 1) or AA (R2 = OH) with

2-(N-ethylperuorosulfoamido)ethyl acrylate (FX-13), R1 = H or
2-(N-ethylperuoro-octane/sulfoamido)ethyl methacrylate (FX-14), R1 = CH3
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+
[230]
NaA, R = O Na+ or
NaAMB, R = C7 H17 N2 O2 Na+ or
NaAMPS, R = C4 H9 NSO3 Na+
1. Terpolymer of sulfur dioxide, N,N-diallyl-N-carboethoxymethylammonium chloride with

N,N-diallyl-N-alkylammonium chloride (R2 = 1) or dendritic quadruple-tailed hydrophobic group
(R2 = 2)
[231234]
Terpolymer of AM and N-(4-butyl)phenylacrylamide (BPAM) with
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
[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
Copolymer of AM (R1 = H) and
[109,138,190,191,236,237]
N-octylacrylamide (OctAM, R = (CH2 )7 CH3 ) or

Diacetone acrylamide (DAAM, R = 1) or
1575
1576
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
3-[tris(trimethylsilyoxy)sily]propyl methacrylate (TMSPMA)
[240]
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
N-methyl-N-(4-ethyl-phenyl)-acrylamide (MeEAM, R = 6) or
BPAM, R = 7
Table 1 (Continued)
Polymer
Structure
References
Amphiphilic
1577
1,1-Dihydroperuorobutyl acrylate (2a) or

1,1-Dihydroperuorooctyl acrylate (2b) or
2-(N-ethylperuorooctanesulfonamido)ethyl acrylate, FOSA (3a) or
2-(N-ethylperuorooctanesulfonamido)ethyl methacrylate, FOSM (3b) or
1,1-Dihydroperuorooctylmono-(ethyleneoxy) acrylate (4a) or
1,1-Dihydroperuorooctylbis-(ethyleneoxy) acrylate (4b) or
1,1-Dihydroperuorooctyltris-(ethyleneoxy) acrylate (4c) or
Dodecyl acrylate (5a) or
Dodecylmono-(ethyleneoxy) acrylate (5b) or
Dodecylbis-(ethyleneoxy) acrylate (5c) or
Dodecyltris-(ethyleneoxy) acrylate (5d) or
Poly(propylene oxide) methacrylate (6)
[132,241243]
Copolymer of AM and
1578
Amphiphilic
1. Copolymer of AM with
[104,244,245]
Model polymer
Copolymer of (AA, R1 = H) or (MAA, R1 = CH3 ) with 2-(1-naphthylacetyl)ethyl acrylate (NAEA) or

2-(1-naphthylacetamido)ethyl acrylamide (NAEAm)
[246,247]
Model polymer
Copolymer of AM with N-[(1-pyrenylsulfonamido)ethyl]acrylamide (APS)
[110,111]
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
Table 1 (Continued)
Polymer
Structure
References
Model polymer
Terpolymer of AM and AA with N-[(1-pyrenylsulfonamido)ethyl]acrylamide (APS)
[177]
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
Model polymer
[235]
1579
1580
Fig. 9. Thermal induced micro-domains [151].
Fig. 10. Schematic presentation of micellar copolymerization [88,135].

monomers per micelle (NH ) [88,109,134,175,258,276]. It

was rst 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 number 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 composition was observed. Therefore, according to the study
[109], the previously thought dissolution of the hydrophobic 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 micellar phase, which modies the reactivity of hydrophobes
[109]. Micelle copolymerization can also be used to synthesize 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 micellar copolymerization technique seems promising, but it
involves using a micelle-forming polymerizable surfactant [114,115,178,179,220,278280]. Although identifying
a correct polymerizable surfactant for the desired molecular structure is difcult, the technique offers the advantage
that purication (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 dened by the template
that is used. A schematic presentation illustrating the template 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 different studies [281285] a longer sequence distribution of
hydrophobic groups can be achieved with this technique.
The molecular weights of the polymers inuence their
behavior in solutions. The molecular weight of HMPAM
remains difcult to determine since intramolecular associations still exist even at very low polymer concentrations.
Fig. 11. Schematic presentation of the template copolymerization technique.
Nevertheless, several different methods have been devised.

These include using the MarkHouwinkSakurada relation for polymers dissolved in water [110,113,114] or
unmodied polymers in the exact same conditions as their
modied analogues [103,229,230,286,287]. However, all
these methods introduce errors in the molecular weight
determination and it would be better to nd a suitable solvent in which the polymer is molecularly dispersed [135].
Several authors reported on formamide as a suitable solvent 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 presence 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 911, having positive and negative charges in
separate building blocks in the backbone, and zwitterionic
monomers 38 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 solution viscosity is a function of the chemical structure and
the solution characteristics (i.e. ionic strength).
From the discussion on the polymers 111 one can
conclude that there are many different advantages of incorporating 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 solubility 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 independent 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 demonstrated to display an enhancement in the solution viscosity
upon addition of low molecular weight electrolytes
[197,201,204,209211,288,289]. This behavior has been
attributed to the shielding of intramolecular Coulombic attraction rather than the intermolecular interactions.
With careful molecular design water-soluble polymers
containing electronic charges can be synthesized exhibiting the required rheological behavior. Peiffer and Lundberg
[289] reported that in order to control the physical properties 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 acrylamide based amphiphilic polyelectrolytes, 1217, have
been synthesized by many different research groups in
search for better thickening polymers in different applications.
Polymers where both charges are incorporated along
with hydrophobic groups have also been studied. These
polymers can be classied as zwitterionic amphiphilics,
1581
1921. 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 salttolerant or responsive to changes in the salt concentration
or ionic strength.
Amphiphilics, 2328, without electronic charges have
been studied extensively for their salt-tolerance. Addition
of salt will not affect the viscosity of the polymer solution since its thickening capability arises from hydrophobic
associations and not from electronic interactions.
The polymers 2933 have been synthesized in order to
enable uorescence 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 associations of the polymer solution: the chemical structure, the
synthesis method, the temperature, the type and concentration of salt and the pH (ionic strength). The following
discussion summarizes the effect of these parameters.
3.1.1. Chemical structure
Generally speaking the rst macroscopic effect of the
polymer chemical structure is observed from the corresponding solubility in water. Indeed, the solubility of
polymer 3 is dependent on the level of AMPDAPS monomer
incorporated [196]. This has a clear inuence on the viscosity of the solution [196] as observed for polymer 5 as
function of the AMPDAE and AMPDAH monomers incorporation 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 understandable on the basis of simple considerations regarding the
overall polarity of the polymeric chains. However, in contrast 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, polymer (10) forms hydrogels and is no longer water-soluble
above 1 mol% incorporation of the charged groups. The carboxylate 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, sulfonate anion in Table 1) exert a clear inuence 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 corresponding copolymer (polymer series 11) classic polyelectrolyte
behavior is exhibited by the solution. However, polymeric solution employing polymers containing equimolar
1582
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 second monomer [211]. Similar to polymer 11, polymer 19
exhibits classic polyelectrolyte behavior when the incorporation 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 associations are present [228].
The presence of hydrophobic groups along the polymer
backbone results generally in the formation of microdomains. 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 distribution. 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 examples 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 polymerization) and 30 are classic examples of a block-like
distribution [111,175,220]. Although the SMR has been
identied as an important parameter for the observed
association behavior, its effect on the composition and
molecular weight of the polymer is minimal as demonstrated 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 solubility 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 polymer as demonstrated with the polymers 12, 15, 17, 18, 23,
24 and 27 (2a, 2b, 3ac and 4ad). 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 uorocarbons instead of hydrocarbons
[212,223,242,269]. The critical polymer concentration at
which hydrophobic associations (critical association concentration, 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 comonomer [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 association 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 intermolecular 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 spacers 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 presence 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 hydrophobic group association at similar length EO spacers. This
behavior has been identied for the aforementioned polymer 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 carboxylate anions) will display the opposite behavior. Polymers
bearing high charge density groups are more susceptible 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 polymer 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 polymer. 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 signicant. 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 display this behavior, not even in de-ionized water and low
pH [176].
A peculiar behavior, in the context of EOR, is the temperature 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].
1583
Fig. 12. Schematic model structure of HMPAM.


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 reptate outside its tube.
In the dilute region (at low polymer concentration)
intramolecular associations dominate [108]. The hydrodynamic 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 networklike 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 modied polyelectrolytes. It has been demonstrated that all
the types of non-Newtonian rheological behavior exist
for these polymer solutions, i.e. pseudoplastic; pseudodilatant; thixotropic; and rheopectic. Application of
shear will, in classical pseudoplastic polymeric solutions, disrupt the hydrophobic associations, which leads
to a reduction in viscosity [88,92,103,109,132]. However this process is reversible, i.e. when the shear is
removed the hydrophobic groups will form new association thus returning the viscosity of the solution up to its
original value [88,92,103,109,132134,136,138,139,242,

257,278,293].
Some associative polymeric solutions display pseudodilatant 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 intramolecular associations are disrupted and the polymeric chains
are extended, which leads to more intermolecular associations [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 pseudodilatant 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 modication
only display the pseudodilatant behavior in the presence
of salt [293,294] while polymers produced using the micellar 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 hydrophobic groups would be different since little control is present
on which functional group is modied. 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 viscosity 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
Fig. 13. Counterion mediated interpolymer associations.

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 disruption by shear will lead to a signicant loss in viscosity
[257]. However as the viscosity is recovered, the shear
induced reduction in viscosity is not due to polymer degradation [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 enhancement 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 signicant 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 behavior 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 behavior 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 uorocarbons 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 polymer 15 [185].
The rheological properties of HMPAM can be, as mentioned before, explained by the balance between intra- and
intermolecular hydrophobic associations. The copolymerization 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 solution viscosity due to their preference for intermolecular
association.
The position of the hydrophobic groups along the backbone 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 placing the hydrophobic group (polymer 24) at the ends of
the polymer is the optimal conguration for obtaining the
highest solution viscosity [245]. According to the authors
the placement of hydrophobic groups along the backbone 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 multisticker) it was demonstrated that the highest thickening
capability, i.e. solution viscosity against polymer concentration 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 concentration 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 dependence of the rheological behavior from the chemical
structure is applicable for uorine 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 incorporation 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
behavior is signicantly suppressed. The shear thickening

is attributed to the breakage of intramolecular hydrophobic 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 signicantly
higher in high salt concentration solution compared to
the other two terpolymers. The strength of the hydrophobic associations depends on the type of groups used. The
terpolymers incorporating carboxylate anions displayed
stronger hydrophobic interactions compared to the polymers 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 thickening 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 rheological 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 hydrophobic block increases in length [299].
3.1.2.2. Effect of external parameters. For neutral associative 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 electrostatic 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 [198200].
The effect of salt on polymers bearing charged moieties 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. intermolecular hydrophobic interactions are dominant rather than the
electrostatic repulsions [221], and thus an enhancement
of the solution viscosity. Classic examples of this behavior (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 (AMDiC6 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 rst, which
is preceded by the addition of salt, a complete different
solution behavior is observed. Diluting a polymer solution (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 solution increases with increasing salt concentration. Fig. 14
presents the three different behaviors. This conrms the
non-equilibrium character of these solutions, but a better
explanation has yet to be provided.
It has been demonstrated that the following surfactants interact with different HMPAM polymers and give,
depending on the surfactant concentration, a higher
viscosity [90,92,115,138,173,287,300302]. The interaction 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 surfactants (SDS [90,92,120,138,173,212,228,243,301305],
potassium dodecyl sulfate (KDS) [212], cetyltrimethylp-toluenesulfonate
[CTAT]
[305,306],
ammonium
dodecyltrimethylammonium chloride [DTAC] [290,300],
hexadecyltrimethylammonium [HTAC] [303,304], CTAB
[90,233], trimethyltetradecylammonium bromide [TTAB]
1586
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], alkylbenzenesulfonates [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 [92,117,120,154,173,300,301,303,304,307309].
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 interchain 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 dependent on the type of surfactant. Two different studies
[303,304] demonstrated that the surfactants hexadecyltrimethylammonium 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] concluded 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 interactions, 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 signicant increase in viscosity. 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
polymerCTAB and polymerCDMAO mixture [90,115].
The transition is believed to be due to the gain in free energy
upon addition of the chemicals where the hydrophobic 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 signicantly 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].
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 viscosity upon the addition of CTAT. Adding salt (NaCl) to this
solution leads to a further increase in the solution viscosity 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 uoro- and hydrocarbon copolymers 12 and surfactants. At low incorporation level of the hydrophobic
groups the interactions with surfactants is selective to surfactants 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 (terpolymer of AMNaAMPSAMPDAC) or 12 (Table 1) is
minimally dependent on the temperature in the range
3060 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 temperature is increased. The intrinsic viscosity of the polymer
solution increased (from 6.5 to 8.5 dl/g) when the temperature is increased from 25 to 60 C [197]. This has
been observed for polymer 14 in the temperature range
of 2040 C. According to the authors [217] the increase
can be attributed to the fact that hydrophobic associations are endothermic in the investigated temperature
range, as hypothesized by McCormick et al. [103]. Using
the latter terpolymers 14 LAlloret et al. [310] observed
a signicant increase in the solution viscosity when the
temperature is increased from room temperature to 80 C.
In addition the authors demonstrated that the thermothickening 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 concentration 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 microdomains. According to the authors the size of the microdomains increase at higher temperatures but their number
Fig. 17. Schematic illustration representing the thermally induced conformational changes.
1588
Fig. 18. Schematic presentation of the effect of solution pH on the network structure.
decreases and causes the aforementioned connectivity

loss.
The viscosity of the AMAMPDAC 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 2560 C). Another polymeric solution that displays peculiar behavior with increase in the temperature
is the solution of terpolymer (9, AMNaAMPSAMPDAC),
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 temperature. However, one important nding 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 thermally 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 intermolecular hydrophobic associations and thus an increase in the
viscosity.
The pH of the polymeric solution also affects the solution 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 opposite 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 signicant increase in the solution viscosity
is observed while at a pH between 5 and 11 the solution 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 56 and 1213 [221].
Although the effect of pH on polyelectrolyte amphiphilics is
complex (vida supra), the investigation of the polymer network 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 conformation of the polymer chains and their associations [218]
(see Fig. 18).
Increasing the pH will lead in principle to the transition 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 preference 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 carboxylic groups leading to (1) intramolecular electrostatic
repulsion and thus chain extension and (2) intermolecular electrostatic repulsion leading to disruption of the
intermolecular associations. The rst effects dominate at
low pH, the latter one at high pH [240]. However, in contrast 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 carboxylic 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-
Fig. 19. Schematic presentation of a hypercoil.

molecular) associations. If the 4-BA content is 70 mol%

only intramolecular associations are present at all ionization 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 hydrophobic associations is suppressed. At low pH, intramolecular
hydrogen bonding stabilizes intramolecular hydrophobic
associations thus excluding intermolecular association.
The transition from closed (intramolecular) to open (intermolecular) associations has been conrmed 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 phenomenon [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
1589
Fig. 20. Schematic presentation of transition to intramolecular association.

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 concentration) 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 modied ethoxylated urethane
(HEUR)
The interest in HEUR focussed on fundamental research
[313] and commercial applications in paint formulation [314,315], paper coating [314,315] and shampoo
Fig. 21. Schematic presentation illustrating the effect of pH and ionic strength.
Reproduced with permission from [226] 2000 and [227] 2000, ACS Publishing.
1590
Fig. 22. Chemical structure HM PEO.
formulation [314,315]. Their use as model compounds can

signicantly increase the scientic understanding of associating polymers. Table 2 presents an overview of the
published systems with the corresponding chemical structure.
HEUR polymers are prepared by chain extension of
poly(ethylene oxide) (PEO) oligomer with a narrow molecular weight distribution (MWD) using di-isocyanate and
end-capping with a hydrophobic group [105]. HEUR polymers 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 corresponding 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 polymer displaying a broad MWD. The procedure for uni-HEUR
involves the direct addition of a mono-isocyanate containing a hydrophobic group to the PEO. To this a hydrophobic
group is added. The resulting polymer has a relatively narrow MWD, which is related to that of the parent PEO. The
chemical structure of a hydrophobically modied 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 signicant 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
uorocarbon containing hydrophobes [186,329331],
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)
[122,125,129,186,318,319,329331,338],
dicyclohexylmethane 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 elucidated using uorescence studies. In principle rosette-like
[124,126,318,319,328] aggregates are formed with diameters in the nanometer range resembling star polymers
[340,341]. The formation of these structures starts above
the critical micelle concentration (CMC) [124]. The rosettelike 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 (approximately 510 looped chains) [130,318,319,342]. The
number of hydrophobic groups present in the hydrophobic 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 solution. 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 223).
Several other publications [105,126,329,338] provided
similar schemes illustrating the different concentration
regimes.
Aside from the independency of the structures on concentration, 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 network depends on the end group as observed with polymer
45 (16).
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 inuence
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
groups (R) employing different diisocyanates moieties (DI).
[89,317]
Given the amount of different reagents used we refer to US Pat. 4,079,028 [317] for the
complete list of reagents.
[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
structure. Either end capped (traditional HEUR polymers, 1) or the hydrophobic end
groups are separated by oxyethylene groups around an internal hydrophobe, 24.
Polyethylene oxide end capped at both sides with an hexadecyl group:
[122]
1591
1592
R = different amine and alcohol containing groups
[189,320]
R = C6 H13 , C8 H17 , C12 H23 , C14 H29 and C18 H37
Polymers based on ethylene oxide:
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
[125]
Polymers based on ethylene oxide using different hydrophobic groups and different
diisocyanate groups. The polymers are either end capped at both sides with internal
hydrophobic groups.
Table 2 (Continued)
Polymer
References
[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)
[124]
Structure
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:
[322325]
Polymers based on ethylene oxide, end capped at both sides with hexyl (N = 5), octyl
(N = 7) or dodecyl (N = 11) using either hexamethylene diisocyanate (HDI) or
bis(4-isocyanateocyclohexyl)methane (H12 MDI) as the diisocyanate group.
[188,326]
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]
Dodecyl alcohol (N = 12) or

Cetyl alcohol (N = 16)
Table 2 (Continued)
Polymer
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
References
[328]
Polymer based on ethylene oxide, end capped at both sides with different alkyl groups:
Structure
1595
1596
Polymer based on ethylene oxide, end capped either at one side (1) or at both sides (2)
with octadecyl groups (1) or with nonylphenol (2) groups:
[187]
Polymers based on ethylene oxide end capped at both sides with uorocarbon
hydrophobes:
[329]
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
uorocarbon hydrophobes.
[186,330,331]
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
Table 2 (Continued)
Polymer
Structure
References
Polymers based on ethylene oxide end capped either at both or one side with
uorocarbon hydrophobes:
[182,332334]
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.
End group: F(CF2 )8 (CH2 )11
[335]
1597
1598
Fig. 23. Concentration regimes of a telechelic PEO.

urethane linkages. The polymer series 49 was synthesized 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 signicant changes in associating 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 signicantly
different association mechanism was observed when comparing comb and telechelic polymers. Comb associative
polymers display a more compact structure in comparison 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, 24). According to the authors [122] this behavior can be attributed
to the dominance of intramolecular hydrophobic associations. To resolve this, the use of SDS was suggested. The
polymer series 38(1) are prepared by step growth polymerization 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 uorocarbon rather than
hydrocarbons, or by increasing the size of the di-isocyanate
group [124,320,329,330]. An example of such a polymer is polymer 41 where increasing the hydrophobicity
Fig. 24. Dimer and micelle formation for polymer 35 (2).

Fig. 25. Superbridges, superloops and dangling ends.
of the end group leads to an enhanced network. It was

demonstrated that the thickening efciency decreased in
the order of octadecyl > pentadecyl > 9-heptadecenyl [124].
The same trend was observed for polymer 43 (2) where
the thickening efciency decreased in the order of dodecyl > octyl > hexyl [188] and for polymer 45 (16) [328].
Polymers 46, 47 and 48 (1 and 2) represent polymers with
increased network strength due to the presence of uorocarbons instead of hydrocarbons.
Several publications presented the rheological properties 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 [89,124,318,328,338,343,345349]. This
relaxation time was attributed to the residence time of
a hydrophobic end (group) inside a hydrophobic microdomain.
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 signicant
increase in viscosity. A further increase in the polymer concentration leads to more micelles. As mentioned
before, these micelles can be interpreted as star-like polymers, which are known to repel each other in good
solvents [89,345347,350]. However, telechelic micelles
have the possibility of forming bridges between two separate hydrophobic cores, thus leading to cluster formation
between them [341]. The viscosity of the polymer solution now changes due to an increase in the hydrodynamic
volume of the micellar clusters formed. Raising the polymer 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. Superbridges 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 entities (Fig. 25).
By using uorescence spectroscopy, it has been demonstrated 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 connecting 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 display 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 pseudodilatant 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 certain 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 ows and proposed a more rened 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 signicant 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 12 and 3 is the mechanism
causing the loss in viscosity. It was demonstrated that in
regions 12 the superbridge network junctions disrupt,
but they rearrange quickly without a loss in the number 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 uid [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 relatively 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 viscosity as a function of the polymer concentration, is lower
when compared to telechelic polymer [89]. The comb associative 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 molecular weight of the comb type is higher than for the telechelic
one. In addition, it was demonstrated that the distribution of the hydrophobic groups plays a crucial role in
the observed behavior. When each of the hydrophobic
moieties consist of two hydrocarbon groups the thickening capability is signicantly enhanced. This is similar to
the behavior observed for twin-tailed HMPAM polymer
1600
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 comparison 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 conicting
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 hydrophobic 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 rheological 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 signicant (static) viscosity increase
is observed is much lower for the difunctionalized polymer. However, it cannot be concluded that this difference
is only caused by the single end capping since the molecular 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 principle, the molecular weight of the HEUR polymer has an
optimal intermediate range where the highest thickening capability can be obtained [331]. The critical polymer
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 viscosity 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 (16) 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 rheological properties of the polymeric solution. A study [325]
compared the thickening capability of the polymers and
found signicant 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 contain small polymer chains of low molecular weight and
these polymers favor the formation of intramolecular
hydrophobic associations. This leads to a weakened polymer 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
[124,164,182,335,353357], DTAB [354], nonylphenol
Fig. 26. Model depicting the effect of shear on the network structure.
1601
Fig. 27. Different aggregates formed with the addition of surfactant.

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 signicantly 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 hydrophobic micro-domains arise can be inuenced 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 solution. The study by Alami et al. [127] provided a schematic
presentation of the interactions between the SDS surfactant 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 difcult to distinguish 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 surfactant is mainly with the hydrophobic ends of the polymer
chains, which leads to a stronger network and thus an
enhanced solution viscosity [124,127,164,182,353356].
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
of the polymer chain has been found [164,182,354356].

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 addition 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 cyclodextrin concentration detachment of the bridging chains
between micelle clusters occurs, which weakens the network 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
Fig. 28. Interactions between cyclodextrins and a HEUR polymer.

3.3. Hydrophobically modied 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 nonionic 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.
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 reservoir water, is benecial for application in EOR. In most
cases the ratio between methacrylic acid and ethyl acrylate (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 modied by the introduction 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 backbone of the HASE polymer chains are favored [169,363].
The backbone of the HASE polymers possesses moderate
high molecular weight and can reach 200,000250,000 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 emulsion copolymerization process [181,363,372]. The three
constituents, methacrylic acid, ethyl acrylate and the
hydrophobic macromonomer, are added to the reaction mixture along with an initiator. The hydrophobic
macromonomers act as the surfactant for the polymerization reaction. These are produced by rst ethoxylating a
hydrophobic group and subsequently reacting the product of the ethoxylation with an unsaturated isocyanate
[363,364,367]. The reaction product of the emulsion polymerization is the HASE polymer.
Different types of hydrophobic groups have been used
which include alkyl groups [106,363,367,369,370], complex poly(alkylaryl) moieties [91,363] and hydrophobic
groups containing pyrene for investigation of the association structures [365,373375].
The length of the PEO groups to which the hydrophobic 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 hydrophobicity 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 structure 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 ow [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 identied, 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
uorescence 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 associate compared to only 5% in tetrahydrofuran (THF). The
same authors demonstrated though, that the coil expansion 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 demonstrated by Tirtaatmadja et al. [367] which is in line with
ndings 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 therefore a stronger network. However, if the length exceeds
a certain critical length intramolecular associations are
favored causing a collapse of the network [169].
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 signicant 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 particles 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 negative 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 conguration of the polymer aggregates. The
thickening capability of the HASE polymers is a combination 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 interactions are present [370]. The intermolecular hydrophobic
interactions give rise to network formation thus enhancing 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
References
[169]
R = H (1), C8 H17 (2), C12 H25 (3), C16 H33 (4) or C20 H41 (5)
m = 33 (for 2)
m = 35 (for 1, 35)
XYZ (1) = 48.7651.240.00 (mol%)
XYZ (2) = 49.0050.001.00 (mol%)
XYZ (3) = 49.0550.050.90 (mol%)
XYZ (4) = 49.0650.040.90 (mol%)
XYZ (5) = 49.0650.040.90 (mol%)
Polymer based on methacrylic acid (MAA), ethyl acrylate (EA) and a hydrophobic
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
XYZ (A&B) = 49.0650.010.90 (mol%)
[106,169,366,367]
Structure
Table 3 (Continued)
Polymer
References
[363,366368]
Structure
m = 80
XYZ = 40.0040.0020.00 (wt.%)
1605
1606
m = 53
XYZ (Refs. [169,369,370]) = 45.0055.00<1.00 (mol%)
XYZ (HASE65) = 0.490.490.021
XYZ (HASE48) = 0.500.490.011
XYZ (HASE42) = 0.440.550.011
XYZ (HASE35) = 0.450.550.006
XYZ (HASE12) = 0.400.590.002
XYZ (HASE11) = 0.400.690.0035
XYZ (HASE0) = 0.400.590.002
[91,371]
1607
Fig. 30. Microstructure as proposed by Dai et al. [369].

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 suspension 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 hydrophobic 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 signicant 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.

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

Reproduced with permission from [378] 2002, John Wiley and Sons.
1608
There are a number of different interactions in

the network of HASE polymers, which are the intraand 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 derivatives as probes. The ethyl acrylate rich micro-domains
(Fig. 33) are what Araujo et al. [180] envisaged.
Most HASE polymer solutions exhibit a strong pseudoplastic behavior when sheared, which is preceded by a
weak shear thickening region [106,378]. The latter arises
due to the disruption of the hydrophobic intermolecular associations by shear [365]. Thixotropic behavior was
also noticed by Knaebel et al. [378], similar to polymeric
solutions containing HMPAM. Increasing the polymer concentration 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, hydrophobicity 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 hydrophobic micro-domains. However if the length of the PEO
spacers surpasses a critical length intramolecular associations 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 highest steady shear and zero shear solution viscosity. The
more pronounced shear thinning and viscoelastic behavior 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 properties. Increasing the hydrophobicity or the length of
the hydrophobic groups will increase the strength of the
hydrophobic associations [169,367,376]. This translates
into a higher steady shear and zero shear solution viscosity 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 network 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 behavior arises by the coexistence of hydrophobic associations
and chain entanglements [371]. Ng et al. [381] investigated the difference in solution viscosity in HASE polymers
compared to the unmodied analogue. Fig. 34 schematically 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 modied polymers compared to the
unmodied analogues is attributed to this enhancement.
As mentioned before the hydrophobicity of the hydrophobic 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 capability 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 incorporation 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-
Fig. 33. Network structure of a HASE polymer.

1609
Fig. 34. Schematic presentation of the associations in HASE and its unmodied 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 emulsion 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 backbone 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 polyelectrolyte 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 viscosity [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 hydrophobic micro-domains of polymer 51 (5) were probed using
pyrene [181]. At a pH of 5.7 a large number of hydrophobic micro-domains are present. As the pH of the polymer
solution is raised a smaller number of larger hydrophobic domains are formed. The authors suggest a transition
from intramolecular to intermolecular hydrophobic associations. This leads to a signicant increase in the solution
viscosity.
Adding salt to the polymer solution affected its rheological 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 concentration [368]. The rst effect, signicant 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 backbone. 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 [91,106,375,382384] have
been published on the interactions between HASE polymers 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] demonstrated that the shear rate range where shear induced
Fig. 35. Model illustrating the network structures of HASE in salt under shear.
1610
Fig. 36. Interactions between nonionic surfactant and HASE polymers.

structuring of the polymer network occurs can be widened.

The use of water-soluble nonionic surfactant, at high sufcient 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 evidence of complete segregation was found. A few studies
[382384]demonstrated the increase in viscosity of the
polymeric solution, employing polymer 51 (5), when using
nonionic surfactant (C12 EO4 ). The increase in the viscosity 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 surfactant 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 (nonionic) 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 concept, i.e. the relation between characteristic relaxation time
and exit rate of hydrophobic groups, as proposed by Aubry
and Moan is controversial and needs verication [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 polymers 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 surfactant. 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 polymer 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 different 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 polymersurfactant interactions
on the rheology are limited. However, in region 3 weakening and destruction of the polymer network arise due to on
one hand shielding of the charges (less electrostatic repulsion 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 behavior of nonionic surfactants discussed earlier. Nevertheless
the same behavior, loss in solution viscosity at high surfactant concentration, has also been reported for a nonionic
surfactant (polyoxyethylene) [106].
3.4. Hydrophobically modied cellulose derivatives
The current demand for environmental-friendly
materials is relevant also for EOR applications. Hydrophobically modied hydroxyethyl cellulose (HM-HEC),
hydrophobicallyhydrophilically modied hydroxyethyl
cellulose (HHM-HEC), hydrophobically modied hydroxypropyl cellulose (HM-HPC) or hydrophobically modied
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 hydrophobically or/and hydrophilically modied to produce the
HM-HEC, HHM-HEC, HM-EHEC or HM-HPC polymers. A
general structure of hydrophobically modied cellulosic
polymer is presented in Fig. 38.
1611
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 reactor is charged with the HEC polymer and isopropyl alcohol
together with an aqueous solution (48%) of sodium hydroxide. 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 synthesis of different HM-EHEC polymers have been developed
and provided by Bostrm 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 analogues. The network structure is enhanced due to these
groups and the hydrophobic associations arise at very low
polymer concentration [118,399,405,407409]. Polymers
56, 57, 58, 61 and 63 are classic examples of this behavior with associations commencing at very low polymer
concentrations. When good solvents are used, e.g. alcohols or dioxane, no associations arise [118]. Polymers 56,
57, 58 and 63 impart a stronger network when compared
to their unmodied analogues. The type of hydrophobic
Fig. 38. General chemical structure of hydrophobically modied cellulosic polymer.
group also affects the strength of the network. Increasing the hydrophobicity will increase the strength. Polymer
57 and 60 (R1 = 2) are examples where the polymer with
uorocarbon provide a stronger network than the hydrocarbon (un)modied analogue [391]. The distribution of the
hydrophobic groups is also of crucial importance. Polymer
62 represents an example in which, due to inhomogeneous distribution of the hydrophobic group, two separate
phases of polymers are observed [401]. One containing
highly substituted chains and another with less substitution. 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].

Although different types of hydrophobically modied
polysaccharides have been synthesized their rheological
properties in aqueous solution depend on the modication rather than on the type of polysaccharide used.
The hydrophobic modications introduced on the different cellulose derivatives decrease the solubility of the
polysaccharide. Several studies have demonstrated the
pseudoplasticity of hydrophobically modied polysaccharides. Typical shear thinning is observed similar to the
hydrophobically modied 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 addition shear thickening behavior is observed. The presence
of shear thickening only arises within a certain concentration range of approximately 0.150.5 wt%. The zero-shear
solution viscosity of a polymer solution is much more
dependent on the concentration in the lower concentration 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
[106]
HHM-HEC, R2 = nC18 H37 and R3 = 1

S-HEC, R2 = H and R3 = 1
R-HEC, R2 = nC18 H37 and R3 = H
HM-HEC
Commercial product, produced by different suppliers.
[386]
The hydrophobic groups are long alkyl chains and the hydrophilic groups are sodium sulfonate
groups.
Table 4 (Continued)
Polymer
Structure
References
HM-HEC
The hydrophobic groups are uorocarbon chains
[386389]
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
HM-HEC
[391]
1613
1614
HM-HEC
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, ourocarbon groups
R1 = 3, cationic groups
R1 = 3 and 4, cationic and hydrophobic groups randomly distributed
R1 = 5, cationic hydrophobic groups
[392394]
R3 , R4 and R5 = alkyl, aryl, aralkyl, alkaryl, cycloalkyl, alkoxyalkyl and alkoxyaryl where a
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.
Table 4 (Continued)
Polymer
Structure
References
HM-HPC
[395,396]
HM-EHEC
The hydrophobic groups are either long alkyl chains or a nonylphenol group
[397399]
The polysaccharide is labeled with pyrene (1) or uorene (2) groups for uorescence studies
1615
1616
HM-HEC-py-1
The hydrophobic groups are an alkyl chain and a pyrene group for uorescence studies
[118,400]
The hydrophobic groups are amino-terminated poly(N-isopropylacrylamide)
[307,401404]
HM-Alginate
The hydrophobic groups are n-octylamines
[405]
HM-CMC
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
[392394].
Thixotropic behavior is also observed for the hydrophobically modied polysaccharides. Similar to other
hydrophobically modied polymers, such as HMPAM,
hysteresis effects can be seen for polymeric solution
employing polymer 55 (HHM-HEC, R-HEC) [387], 56 [412],
58 [392394], 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 modied polysaccharides display 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 modied polymers associations
between the hydrophobic groups arise which lead to a
strong polymer network. The behavior, signicant increase
in the zero-shear viscosity, was noticed for solutions
employing either polymer 58 [392394] or polymer 64
[405].
As mentioned before, the incorporation of charged
moieties affects the network structure of HHMpolysaccharides. 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 incorporated into the backbone of the HM-polysaccharides, screening 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 signicant reduction
in the solution viscosity. However, for the polysaccharides modied 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 hydrophobic 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 substitution signicantly affects the solution properties at
low polymer concentration [389]. The thickening capability is increased when this ratio is high. Polymer 55
is an example of a polymer whose thickening capability
increases with a high hydrophobic/hydrophilic substitution [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 electrostatic repulsion is reduced. This leads to a reinforcement
of the hydrophobic associations and thus a stronger polymer 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 hydrophobic 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 presented 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 concentration 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 hydrophobically modied polysaccharides. In most cases the viscosity
is reduced as the temperature is increased. This behavior 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 viscosity 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 modied polysaccharides also display interactions with different types surfactants, i.e.
anionic, cations or nonionic. The surfactants that have
been demonstrated to interact with hydrophobically
modied 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 interact with the hydrophobic groups forming mixed micelles.
The formation of these mixed micelles will increase
the number of hydrophobic microdomains and will
1618
Fig. 39. Schematic model of the effects of added salts.

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 subsequently a drop in the solution viscosity of the ternary
(waterpolymersurfactant) system [423]. The viscosity
of the polymeric solution employing polymer 55, 57,
62 (R=1) or 65 increases and passes through a maximum 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 polymersurfactant solution employing a surfactant with a lower CMC will reach a maximum
solution viscosity at lower surfactant concentration compared 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 polymersurfactant solution leads at rst to a reduction 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 cooperative binding [417,426] similar to the unmodied analogue
(EHEC) in polymersurfactant solution [426]. In addition, the data indicate that the number of hydrophobic
microdomains is constant with respect to the surfactant 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 Nystrm [419] demonstrated that the association complexes 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 concentration 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, Thuresson et al. [425] demonstrated that the solubility of the
Table 5
The different surfactants shown to interact with hydrophobically modied polysaccharides.
Surfactant
Abbreviation
Type
Source
Sodium dodecyl sulfate

Sodium decyl sulfate
Sodium tetradecyl sulfate
Sodium dodecyl-di(ethyleneoxide)-sulfate
Sodium alkanoate
Sodium octyl benzene sulfonate
Cetyltrimethylammonium bromide
Tetradecyltrimethyl ammonium bromide
Dodecylammonium chloride
Dodecyltrimethylammonium chloride
Dodecyltrimethylammonium bromide
Hexadecyltrimethylammonium bromide
Hexadecyltrimethylammonium acetate
Alkyl betainate
Octylphenol adduct
Polyoxyethylene alkyl-ether
SDS (NaC12 S)
NaC10 S
NaC14 S
(NaC12 [EO]2 S)
CH3 [CH2 ]n COONa, n = 4, 6, 8 and 10
SOBS
CTAB
TTAB
C12 ACl
C12 TACl
C12 TABr
C16 TABr
C16 TAAc
CH3 [CH2 ]n COOCH2 N[CH3 ]3 , n = 9, 11, 13
C8 H17 C6 H4 O[EO]10 H (Triton X-100)
Cm Hn , m = 11, 12 and 13/n = 4
Anionic
Anionic
Anionic
Anionic
Anionic
Anionic
Cationic
Cationic
Cationic
Cationic
Cationic
Cationic
Cationic
Cationic
Nonionic
Nonionic
[117,307,408,416428]
[117]
[424]
[424]
[427]
[427,429]
[430]
[420,430]
[424]
[424]
[424]
[424]
[424]
[431]
[418]
[117,415,420]
hydrophobically modied polymer is suppressed at low

SDS concentrations compared to its unmodied 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 associations at moderate surfactant concentration. Increasing
the surfactant concentration further leads to the disruption of the hydrophobic micro-domains and thus of the
polymer network. According to Kjonikson et al. [434] the
polymersurfactant 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]. Nevertheless, 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 inuence of a spacer (EOspacer) between the hydrophobic group and the polymer
backbone on the solution viscosity [434] in the presence of
surfactants. At high surfactant concentrations, the behavior of the polymer with or without the spacer is similar to
its unmodied non-hydrophobic analogue. The viscosity of
the polymeric solution employing the HM-EHEC with spacers 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 HogenEsch [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 properties 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 viscosity which is higher than for a solution without the
surfactant.
1619
chemical/molecular structure. Rheological properties will

be affected by a combination of external parameters and
the chemical nature and molecular structure of the polymer. For instance, the rheological properties of an aqueous
solution of an amphiphilic polyelectrolyte are similar to
those of an unmodied analogue without amphiphilic
moieties. However, in the presence of salt a markedly different behavior is observed. The solution viscosity of the
unmodied polymer decreases with increasing salt concentration, whereas the solution viscosity of the aqueous
solution containing the amphiphilic polyelectrolyte is not
affected. Another good example is the thermal performance of amphiphilic polymers: the rheological properties
of an aqueous solution containing the amphiphilic polymer or its unmodied analogue, i.e. without the NIPAM
monomer, are quite similar. However, when exposing both
solutions to higher temperatures signicant 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 unmodied analogue
changes signicantly.
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 differences in the agglomeration principles governing their
water behavior. On a molecular level the basic principle is indeed quite general: the presence of relatively
weak inter(macro)molecular interactions (e.g. hydrophobic association and hydrogen bonding) factually increases
the molecular weight of the polymer coils. As a consequence the solution viscosity increases. However, a
careful balance must be observed here since predominantly weak interactions (both in terms of strength and
number thereof) do not result in observable rheological differences while excessively strong ones might compromise
the solubility of the system by leading for example to gel
formation.
Acknowledgement
4. Conclusion
This review clearly indicates that the successful design
of new water-soluble polymers for a given application requires an integral multiscale and multidisciplinary
approach. Proper denition of the required product properties 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. polymer architecture and overall chemical composition) of the
corresponding water solution.
The inuence of external parameters (e.g. pH and temperature) 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 dened only as a function of the
This work is part of the Research Programme of the

Dutch Polymer Institute DPI, Eindhoven, the Netherlands.
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Progress in Polymer Science 36 (2011) 15581628

Contents lists available at ScienceDirect

Progress in Polymer Science

Polymers for enhanced oil recovery: A paradigm for

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 15581628

critical micelle concentration

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 15581628

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 15581628

high temperatures (>70 C) and long injection times (at

2. Currently used EOR polymers

Fig. 1. Chemical structure of HPAM.

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 15581628

has been presented as a solution to the salt sensitivity of the

Fig. 2. Complexation behavior of HPAM under different conditions.

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 15581628

Fig. 3. Schematic presentation of behavior of HPAM coils in shear ow.

viscosity [42]. Another parameter that affects the solution

fore the entanglements, related to the solution viscosity,

Fig. 4. Type I and II of rheopectic behavior of HPAM solutions.

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 15581628

mono-valent cations is amplied, i.e. the effect is seen at

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 15581628

Fig. 6. Chemical structure of xanthan gum.

2.3. Xanthan gum

tions employing xanthan gum display high viscosity at

Fig. 7. Conformational transition of xanthan gum.

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 15581628

[83,84]. However the use of biocides to protect the xanthan

3. Recent developments in water-soluble

Fig. 8. Intra- and intermolecular associations.

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 15581628

in turn yields a polymer with a much better thickening

3.1. Hydrophobically modied polyacrylamide (HMPAM)

Copolymer of acrylamide (AM) and sodium 2-acrylamido-2-methylpropanesulfonate (NaAMPS, R = 2)

Copolymer of acrylamide (AM) and sodium 3-methacrylamido-3-methylbutanoate (NaMAMB)

Polyelectrolyte, zwitterionic monomer

Polyelectrolyte, zwitterionic monomer

Copolymer of acrylamide (AM) with

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 15581628

Polyelectrolyte, zwitterionic monomer

Copolymer of AM with 2-(2-acrylamido-2-methylpropyldimethylammonio) ethanoate (AMPDAE,

Terpolymer of AM with acrylic acid (AA) and AMPDAPS

Polyelectrolyte, zwitterionic monomer

Terpolymer of AM with sodium acrylate (NaA) and AMPDAB

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 15581628

Polyelectrolyte, zwitterionic monomer

Polyelectrolyte, zwitterionic monomer

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

Polyelectrolyte, zwitterionic backbone

Polyelectrolyte, zwitterionic backbone

Polyelectrolyte, zwitterionic backbone

Copolymer of 2-acrylamido-2-methylpropanesulfonate (NaAMPS) with

Copolymer of AM (R1 = NH2 ) and sulfonate containing monomer (R2 = 1)

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 15581628

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

A, Dodecylacrylamide (C12 AM), R = NH, M = 11, N = 0 or

Terpolymer of AM (R1 = NH2 ) and AA (R2 = OH) with

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 15581628

Copolymer of NaA and

Terpolymer of AA and methacrylamide (MAM) with

Copolymer of AM (R1 = NH2 ) and dimethyldodecyl(2-acrylamidoethyl)ammonium bromide (DAMAB,

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

D.A.Z. Wever et al. / Progress in Polymer Science 36 (2011) 15581628

(DiC6 AM, N = 4) N,N-dihexylacrylamide or