Polymeric surfactants for enhanced oil

recovery: A review
. Author links open the author workspace.PatrizioRaffaOpens the author workspaceOpens the
author workspace. Author links open the author workspace.Antonius A.Broekhuis. Author links
open the author workspace.FrancescoPicchioni
Department of Chemical Engineering - Product Technology, University of Groningen,
Nijenborgh 4, 9747 AG Groningen, The Netherlands
https://doi.org/10.1016/j.petrol.2016.07.007Get rights and content
Open Access funded by VSNU
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Abstract
Chemical enhanced oil recovery (EOR) is surely a topic of interest, as conventional oil resources
become more scarce and the necessity of exploiting heavy and unconventional oils increases.
EOR methods based on polymer flooding, surfactant-polymer flooding and alkali-surfactant-
polymer flooding are well established, but new challenges always emerge, which give impulse to
the search for new solutions. Polymeric surfactants represent a very attractive alternative to these
techniques, because they can provide simultaneously increase in water viscosity and decrease in
interfacial tension, both beneficial for the efficiency of the process. The analysis of the literature
shows that the use of polymeric surfactants as displacing fluid has the potential to improve the
performances of EOR in some cases. However, the synthesis are often challenging and costly
and the available data about the real performances of such systems in oil recovery are still sparse.
This holds back the possibility of a significant use of polymeric surfactants for EOR. This review
collects the relevant work done in the last decades in developing and testing polymeric
surfactants for EOR, with a particular emphasis on the chemical aspects, the patent literature and
bio-based systems.

Abbreviations
AA
acrylic acid
AM
acryl amide
ASP
alkali-polymer-surfactant flooding
BA
butyl acrylate
Ca
capillary number
DLS
dynamic light scattering
EA
ethyl acetate
EOR
enhanced oil recovery
HMPAM
hydrophobically modified poly(acryl amide)
HPAM
partially hydrolized poly(acryl amide)
IFT
interfacial tension
M
mobility ratio
PAM
poly(acryl amide)
PEO/PEG
poly(ethylene oxide)
PPO
poly(propylene oxide)
PVA
poly(vinyl alcohol)
SP
polymer-surfactant flooding
VA
vinyl acetate

Keywords
Polymeric surfactants
Amphiphilic polymers
Enhanced oil recovery
Chemical EOR
SP flooding
ASP flooding

1. Introduction
Chemical methods for enhanced oil recovery (EOR) consist of the injection of a displacing fluid
in oil reservoirs to mobilize the crude oil trapped in the porous rocks. The displacing fluid
generally is a water solution containing various additives. Typically, the mixture contains a water
soluble polymer (this technique usually is referred to as polymer flooding), alone or in
combination with a surfactant (surfactant-polymer flooding, or simply SP flooding) and/or an
inorganic base (alkali-surfactant-polymer flooding, ASP). All these techniques have been
extensively described in books and review articles (Lake, 1989; Green and Willhite, 1998;
Thomas, 2008; Alvarado and Manrique, 2010; Sheng, 2010; Nazar et al., 2011; Olajire, 2014).
The polymer is used to increase the viscosity of the water, while the surfactant acts as emulsifier.
The scope of the base (generally a hydroxide such as NaOH or a carbonate) is essentially the
same as the surfactant: the base reacts with the organic acid components contained in acidic
crude oils, forming surfactants in situ (Thomas, 2008). Also, besides generating the surfactants,
alkali are added to reduce the adsorption of anionic surfactants on certain rock matrix. Many
studies discuss about the issue of anionic surfactants adsorption on positively charged clay edges
in sandstones and positively charged matrix in carbonate surfaces at neutral pH. This issue is not
treated in detail in this review, but the interest reader can refer to other more specific reviews on
the topic (Olajire, 2014; Hirasaki et al., 2011).

The mechanism of enhanced recovery involved in polymer flooding is based on decreasing the
mobility difference between displacing and displaced fluids, in order to reduce fingering effects.
The displacing phase should have mobility equal to or lower than the mobility of the oil phase
(Ezell and McCormick 2007; Rashidi et al., 2010). When the water/oil mobility ratio (M) is 1 or
slightly less, the displacement of the oil by the water phase will occur in a piston-like fashion. By
contrast, if M is greater than 1, the more mobile water phase will finger through the oil, causing a
breakthrough and poor recovery. Since the mobility is inversely proportional to the viscosity, the
polymer should act as an effective viscosifier for the aqueous phase. The main features of such
polymers are: very high molecular weight, resistance to mechanical degradation in shear and, of
course, complete solubility in water. Additionally, they should be inexpensive, non-toxic and
able to tolerate high salinity and high temperatures. The polymeric systems traditionally
employed for EOR have been extensively reviewed recently (Wever et al., 2011).

In surfactant flooding, the recovery mechanism is based on lowering the interfacial tension
between the two phases (IFT). The role of IFT in oil recovery is better explained in terms of
capillary number (Ca), as discussed in more detail in the next section of this review. The state of
the art of surfactant flooding has been reviewed recently (Hirasaki et al., 2011).

In EOR processes which combines the two mentioned mechanisms, (SP or ASP flooding), some
factors should be considered, such as interactions between polymer and surfactant, loss of
surfactant through solubilization in the oil phase or adsorption on the rocks and chromatographic
separations of the various components, which could be detrimental for the whole process (Sheng,
2010).

For these reasons, the possibility to combine the positive effects of polymers and surfactants in
only one component, namely a polymeric surfactant, becomes an attractive alternative for the
traditional EOR processes. Indeed, the potential of polymeric surfactants for EOR has been often
claimed (Ezell and McCormick, 2007; Winnik and Yekta, 1997; Shaikh et al., 1999; Crevecoeur
et al., 1999; Al-Sabagh, 2000; McCormick et al., 2006; Busse et al., 2002; Desbrieres and Babak,
2010; Sun et al., 2010; Elraies et al., 2011; Fischer et al., 2001; Raffa et al., 2015).

It is very interesting to note that, in a way, polymeric surfactants have been used since long time
in EOR, without really recognizing them as such. The idea of introducing hydrophobic groups in
a water-soluble polymer, which actually makes it a polymeric surfactant (see next section), has
been applied in EOR (Wever et al., 2011; Taylor and Nasr-El-Din, 1998). Several structures
based on hydrophobically modified polyacrylamide (HMPAM) or polysaccharides have been
proposed and even patented (Wever et al., 2011; Taylor and Nasr-El-Din, 1998). However, the
hydrophobic groups are introduced mainly to alter the rheology of the system: it has been
observed that the hydrophobic domain can form shear-dependent transient association in water
with subsequent solution thickening (Winnik and Yekta, 1997; Taylor and Nasr-El-Din, 1998;
Kudaibergenov and Ciferri, 2007). The focus is usually on the effect of hydrophobic interactions
(Wever et al., 2012, 2013a, 2014) or of the chemical structure (Wever et al., 2013b, 2013c,
2013d) on the rheology, while a study of the surface properties is usually neglected. Actually, the
presence of hydrophobic parts in water-soluble structures is also known to affect the interfacial
properties (surface tension, IFT, wettability). Therefore, even if for polymeric surfactants the
effect is usually less pronounced than for low-molecular weight surfactants (Raffa et al., 2015),
this aspect should be considered when hydrophobically-modified polymers are investigated as
potential systems for EOR.

Very general and complete reviews about EOR and traditional polymeric systems used for this
application can be found elsewhere (Lake 1989; Green and Willhite, 1998; Thomas, 2008;
Alvarado and Manrique, 2010; Sheng, 2010; Nazar et al., 2011; Wever et al., 2011; Taylor and
Nasr-El-Din, 1998). Here, we will consider polymeric surfactants that have been proposed for
EOR, especially from the point of view of their interfacial properties. First, the relevant
properties of polymeric surfactants for EOR will be discussed, then the available literature on the
systems proposed, both in the open and in the patent literature will be presented.

In the conclusions and outlook section, the current issues, perspectives and some general criteria
for the selection of potential new candidates to be employed as polymeric surfactants for EOR
will be given.

2. Requirements of polymeric surfactants for EOR

Polymeric surfactants are macromolecules which contain both hydrophilic and hydrophobic parts
in their structure. Compared to traditional surfactants, the macromolecular nature of these
systems allows a much larger variety of structures. For example, a polymeric surfactant can
simply be derived by the polymerization of a surface-active monomer (in this case they are
usually known as polysoaps) or by the copolymerization of an hydrophobic and a hydrophilic
monomer. In this latter case, the distribution of monomers can be varied. This kind of
copolymers can thus have a random, a gradient, or a block structure. Amphiphilic diblock
copolymers are basically the macromolecular transposition of low-molecular weight surfactants
and, consequently, they are commonly referred to as “macrosurfactants” (Raffa et al., 2015).
Moreover, not only linear structures are possible, but also polymeric surfactants with more
complex architecture can be made (graft, star, dendrimers, etc.).

Polymeric surfactants usually present very interesting rheological and interfacial properties
(Raffa et al., 2015). Logically, most of these properties will derive from their chemical structure.
For example, polysoaps are known to have good emulsification properties, but poor solution
viscosity, while macrosurfactants, especially the ones containing a polyelectrolyte block, present
excellent gelation properties but low surface activity (Raffa et al., 2013, 2014). Without
discussing the details, these characteristic derive mostly from the mechanisms of aggregation in
solution. The chemical composition is also very important in determining the final properties. A
very important feature of some polymeric surfactants is the possibility to tune their
hydrophobicity, and thus their aggregation behavior, by changing external parameters, such as
pH, temperature or electrolytes concentration. These kinds of polymers are important building
blocks for smart materials. Of course, depending on the application that one has in mind, some
structures will be more suitable than others.

For all these reasons, polymeric surfactants attracted a lot of interest for actual or potential
applications in several fields including (mini)emulsion polymerizations, coatings, biotechnology,
medicine, pharmacology, cosmetics, agriculture, water purification, electronic, optoelectronic
and enhanced oil recovery (Winnik and Yekta, 1997; Kudaibergenov and Ciferri, 2007; Kwon
and Kataoka, 1995; Alexandridis, 1996; Torchilin, 2001; Adams et al., 2003; Popot et al., 2003;
Gil and Hudson, 2004; Taubert et al., 2004; Rodriguez-Hernandez et al., 2005; Garnier et al.,
2006; Kudaibergenov et al., 2006; Dai et al., 2008; York et al., 2008; Blanazs et al., 2009; Jiang
et al., 2009; Zhou et al., 2009; Zhou and Yan, 2009; Tadros, 2009; Durand and Marie, 2009;
Cayre et al., 2011).

The importance of solution rheology for EOR is mostly connected to the need of adjusting the
mobility ratio by increasing the water phase viscosity, as it has been already emphasized in the
introduction. This applies in a general way for polymer flooding. In surfactant flooding, the
displacing water solution needs to be able to create a stable emulsion with the oil in flow
conditions. Theoretically, it is well established that the process of emulsion formation in laminar
flow is governed by the balance between the viscous force acting on a drop in a laminar flow
field and the Laplace pressure (Walstra, 1993; Grace, 1982). The dimensionless ratio between
the viscous-to-capillary forces is called Capillary number (Ca). This parameter has been related
to the residual oil saturation in porous media and thus it is very important for EOR applications
(Lake, 1989; Sheng, 2010). The capillary number can be defined for several purposes. For EOR
it is convenient to base the calculation on the force balance on a drop of oil squeezed through a
pore throat Reed and Healy (1977). In this case we have:

where is the gradient pressure, is the interfacial tension between the two immiscible phases
(often also indicated with IFT) and k is a constant. According to Darcy's law the equation can be
rewritten as:
where ηc is the viscosity of the continuous phase and v is the Darcy velocity. Other formulations
of Ca have been proposed, which take into account parameters such as porosity, relative
permeability and contact angle, but this form is the most used because of its simplicity.

Typical Ca in waterflooding are in the order of magnitude of 10−8–10−7. It is generally assumed

that for a substantial increase in oil productions the Ca values should be increased by at least 2–3
orders of magnitude, meaning that surfactants should be able to give low to ultralow values of

(γ≤10−1 mN/m) (Green and Willhite, 1998; Iglauer et al., 2010; Abrams, 1975).

The use of polymeric surfactants could represents a favorable option since in principle a decrease
in interfacial tension and an increase in viscosity are expected to occur at the same time, with a
subsequent positive effect on Ca. Moreover, being a polymeric surfactant a single component
and not a mixture, this approach should also have the advantage of avoiding the segregation into
two phases that can occur in a flow stream for conventional polymer-surfactant mixtures (Sheng,
2010; Nazar et al., 2011; Elraies et al., 2011).

The choice of a suitable system on the basis of the above considerations is not trivial. For
example, several polymeric surfactants show very low or even negligible surface activity
(Jacquin et al., 2010; Theodoly et al., 2009; Jacquin et al., 2007; Ghosh et al., 2011; Nayak et al.,
2011; Kaewsaiha et al., 2005; Matsuoka et al., 2004). This lack of surface activity is usually
explained with a very slow equilibration of polymeric surfactant micelles (the so-called “frozen”
micelles (Theodoly et al., 2009)), which prevent the possibility of the macromolecules to migrate
to the interfaces. As clearly documented in literature (Raffa et al., 2015), the structure and the
composition of amphiphilic polymers are fundamental to determine surface properties and
rheology of their aqueous solutions. Also, the physical properties and behavior can be greatly
affected by pH, temperature, presence of dissolved salts and kind of flow.

Other hardly quantifiable characteristics that a suitable polymeric surfactant should possess, are
the same as for traditional polymers for EOR: low adsorption on the rocks, high thermal stability
and salt tolerance.

3. Polymeric surfactants for EOR

The idea to use polymeric surfactant for EOR, which can in principle act either as solution
thickeners and surfactants, is not new. Indeed, most of the systems successfully employed or
proposed as solution thickeners based on hydrophobically modified water soluble polymers
(recently very extensively reviewed 11) can in principle also act as surfactants, although the
surface activity of such systems usually is not considered in the studies (see introduction). In
order to improve interfacial activity and ability of polymer to solubilize and emulsify crude oil,
the surfactant-containing mixtures, such as SP or ASP flooding systems were developed.
However, due to the different properties, such mixtures often separate into two phases in a flow
stream. Other problems can be attributed to the attraction of surfactant to rock-water interface,
which can result in the loss of surfactant to reservoir rock surface by adsorption (Yu et al., 2008),
or to the incompatibility between surfactant and polymer, resulting in the decline of polymer
properties, such as aggregation, adsorption, and diffusion performance in porous media (Sun et
al., 2010). Moreover, in cases where ASP flooding has proven to successfully increase oil
recovery in the field, the presence of the strong alkali has detrimental effects on polymer
performance. In many cases additional polymer is required to achieve the desired viscosity
(Elraies et al., 2011), although it is believed that the alkali positively affects the process, as
briefly discussed in the introduction.

A polymeric surfactant that combines the high viscosity of a polymer with the interfacial
property of a conventional surfactant could reduce the tension at water/oil interfaces and enhance
the viscosity of the aqueous solution simultaneously (Cao and Li, 2002).

Such an approach has already been applied in some fields but, because it is often observed that
polymeric surfactants have only a slight ability to decrease the IFT, relatively few use of
polymeric surfactants in EOR have been reported. However, the common belief that ultralow
IFT (order of magnitude of 10−3 mN/m) values are needed for good performance in EOR has
been recently questioned. Zhang et al., (2010) Some recent SP flooding experiments (Yu et al.,
2010) showed that in some cases there is not a straightforward correlation between lowering the
IFT and recovery, but there is rather an optimum IFT, which is higher than the stated ultralow
values (Fig. 1). The claim that ultralow IFT values are not strictly necessary to improve oil
recovery seems to be supported also by a very recent study, dealing with a polymeric surfactant
rather than a SP mixture: here, a surface active modified HPAM solution with a measured IFT of
10−1 mN/m, gives ~5% more oil recovery than a conventional HPAM in a core-flood experiment,
at even lower viscosity (Co et al., 2015).

1. Download full-size image

Fig. 1. Relationship between incremental recovery and IFT in SP flooding experiments.

Reprinted with permission from Ref. (Yu et al., 2010).

Several papers (Shaikh et al., 1999; Crevecoeur et al., 1999; McCormick et al., 2006; Busse et
al., 2002; Fischer et al., 2001; Theodoly et al., 2009; Qin et al., 1994; Iddon et al., 2004; Yahaya
et al., 2001; Kudaibergenov, 1999; Dimitrov et al., 2007; Jain and Bates, 2003; Hietala et al.,
2007; Zaroslov et al., 2005; Liu et al., 2007; de la Fuente et al., 2005) published in scientific
journal propose various amphiphilic polymers as systems for EOR. Despite this, only few studies
cover experiments performed to prove the effectiveness of such systems for the claimed
application. We could identify few papers in which viscosity, surface properties and salt effects
are taken into account for the evaluation of a given polymeric surfactant in EOR performance.

In one of the first published studies on EOR concerning simultaneously optimization of

rheological properties and interfacial behavior of amphiphilic polymers, alternating copolymers
of alkenes and maleic anhydride were prepared by free radical polymerization and hydrolyzed to
obtain an anionic polysoap (Yahya and Hamad 1995).

Surface and interfacial activities (water vs n-decane) are good (45.0 and 8.68 mN/m
respectively) and IFT decreases in the presence of salt (1.05 mN/m at1 wt% NaCl concentration;
at higher salt concentration, a salting-out effect is present). However, the viscosity of the
solutions is moderate even at high polymer concentrations, because intramolecular aggregations
are predominant, as usually happens for polysoaps. When 1-hexadecene is used as co-monomer,
results in terms of both viscosity and interfacial activity are better compared to 1-dodecene, due
to the increased hydrophobicity. An analogous increase in interfacial activity upon addition of
NaCl was observed for a viscosifier based on hydrophobically modified PVA (Yahya et al.,
1996). Also in this case, an optimization study to maximize both surface activity and viscosity
has been performed.

Good viscosifying properties and surface tension reduction have been obtained with amphiphilic
block copolymers based on Polystyrene-b-poly(sodium methacrylate), containing a PEG-acrylate
comonomer in the hydrophilic block, synthesized by ATRP (Raffa et al., 2016). The presence of
the charged sodium acrylate is necessary to achieve high viscosity, while the PEG moiety
ensures the lowered surface tension. In presence of NaCl, the viscosity decreases due to
electrostatic interactions, but a better surface activity is also measured.

As anticipated, even if their surface and interface properties received little or no attention,
hydrophobically modified water soluble polymers, extensively used as solution thickeners in
EOR, can also act as polymeric surfactants. For example, the introduction of 1% of hydrophobic
acrylates in a polyacrylamide strongly increases the stability of water/oil emulsions (Fig. 2)
(Zhao et al., 2009).

1. Download full-size image

Fig. 2. Emulsion stability of water/oil mixtures with added hydrophobically modified PAM.
Adapted with permission from Ref. (Zhao et al., 2009).

An analogous polymer is capable of stabilizing water/n-heptane and water/oil mixtures, even in

the presence of NaCl and NaOH in a simulation of ASP flooding formulation (Sun et al., 2010).

PAM containing 2–3 wt% N-phenethylacrylamide units distributed in a blocky way shows a

decrease of surface tension as well as a decrease in interfacial tension between water and n-
decane. Interestingly, the polymer containing the lowest number of hydrophobic groups is more
effective in reducing the surface tension, but is less effective in decreasing the interfacial tension.
This has been explained by the authors with the consideration that for higher numbers of
hydrophobic groups, the polymer's ability to form intramolecular aggregates increases as well,
determining a major stabilization in solution and consequently a minor adsorption at the
interface. The reverse behavior in IFT measurements has been explained by the good
solubilization ability of the hydrophobe by n-decane, which provides the hydrophobes with a
more favored environment than the air phase and the hydrophobic aggregates. As a result, the
hydrophobes adsorb at the interface as much as they can in the absence of competition by
hydrophobic aggregation. Self-aggregation also helps to explain the reduced surface activity at
high polymer concentrations (Abu-Sharkh et al., 2001).

The nature of the hydrophobic groups seems to play a crucial role in interfacial activity. Multi-
block (with a random distribution of blocks) copolymer of acrylamide (AM) with styrene
(Shaikh et al., 1999), phenylAM (Abu-Sharkh et al., 2003) and benzylAM (Yahaya et al., 2001)
showed different surface behavior. Apparently, the higher is the conformational freedom of the
monomer (PhenethylAM>benzylAM>phenylAM>sty), the lower is the interfacial activity (Abu-
Sharkh et al., 2001). All these AM based polymers showed interesting salt effects: viscosity and
interfacial activity in presence of added NaCl are unaffected or in some cases improved. Their
properties make these polymers of potential interest for oil recovery.

Amphiphilic phenol-amine-formaldehyde resins (Fig. 3) were evaluated as systems for oil

reclamation from soil. Results with both asphaltenic and waxy crude oils show that the amount
of reclaimed oil is related to the IFT (Al-Sabagh et al., 2003) However, these can be considered
more as oligomeric surfactants (Mw=1000–5000).

1. Download full-size image

Fig. 3. Structure of the polymer studied in Ref. (Al-Sabagh et al., 2003) (redrawn with
permission).

Oligomeric polyesters (structure depicted in Fig. 4) have been prepared and studied for
applications in EOR, proving to be suitable systems because of the ultralow IFT values (Al-
Sabagh 2000).
 1. Download full-size image

Fig. 4. Structure of the polymer studied in Ref. Al-Sabagh (2000) (redrawn with permission).

A direct evaluation of the performance of polymeric surfactants in enhanced oil recovery is

rarely found in literature. Traditional HPAM and hydrophobically modified ones (HMPAM)
have been compared in core flood experiments (Lai et al., 2013; Maia et al., 2009). However, in
those experiments, the viscosity of the HMPAM solutions are higher than the HPAM ones,
which makes impossible to determine if the lowered interfacial tension (not measured) due to the
presence of hydrophobic groups plays a role in the improved recovery. The authors only
observed that the modified polymers present a better resistance to salt and thermal degradation.

A more convincing evidence of the role played by the IFT of a polymeric surfactant in oil
recovery comes from a very recent research (Co et al., 2015). The authors compared the
performance in core-flood experiments of a traditional HPAM and a HPAM modified
incorporating 1–5% of a “surfactant-like monomer” (chemical structure not specified). In this
study it is shown a positive effect of the reduced IFT (10−1 mN/m) on the oil recovery, even if the
polymeric surfactant solution in this case has lower viscosity and thus a less favorable mobility
ratio than the HPAM.

An interesting concept has been proposed by Zou et al. They prepared a PAM containing
cyclodextrin side groups (Fig. 5), claimed as a system for SP flooding. Their hypothesis is that
the cyclodextrin side groups should form inclusion complexes with the surfactant molecules,
preventing their loss during flooding experiments. Also, a synergistic effect has been suggested,
since the oil phase can displace the surfactant in the hydrophobic cavity of the cyclodextrin, with
subsequent “controlled” release of the surfactant molecules. Of course, the concept still needs to
be proved and it seems to be hardly applicable from a practical point of view, also due to the
high costs of cyclodextrin containing acrylic monomers.
 1. Download full-size image

Fig. 5. Structure and proposed mechanism of action of cyclodextrin-substituted PAM. Adapted

with permission from Ref. Zou et al. (2011).

3.1. Patents

Several patents concerning EOR and related applications of amphiphilic polymers have been
deposited (van de Kraats and Sawyer, 1976; Byham et al., 1980; Chen and Sheppard, 1982,
1981; Evani, 1989; Huff et al., 2008, 2011; Savu and Sierakowski, 2010; Hough et al., 2010;
Caneba, 2010; Favero and Gaillard, 2010; Zhang and Tang, 2010; Soane et al., 2011), focusing
on their effects on both viscosity and interfacial tension between water and oil. A list is given in
Table 1. Formulations can include the use of low molecular weight co-surfactants. For author's
choice, oligomeric surfactants are not considered here.

Table 1. List of patented polymeric surfactants for EOR.

 Ref Chemical composition Structure
Triblock copolymer
Mw
hydrophilic=100–
(van de
2000 kDa
Kraats and
Mw
Sawyer, 1976)
hydrophobic=1–10 
kDa

(Byham et al., Diblock copolymer

1980) Mw>50 kDa

1:1 Statistic
copolymer
20–40%
functionalized
(Chen and
Sheppard, Mw=3800 kDa
1982, 1981)

Multiblock
Mw~103 kDa
(Evani, 1989)

(Huff et al., Comb, multiblock,

Broad range of block copolymers
2008, 2011) star
Rf=fluoroalkyl
(Savu and R1=alkyl
Sierakowski, Random
2010) Mw>100 kDa

Diblock
3 kDa (styrene)
(Hough et al., +30 kDa (total
2010) acrylates)
 Ref Chemical composition Structure

(Caneba, Tapered,
2010) ammonium salt

0.4%
(Favero and
hydrophobically
Gaillard,
modified 25%
2010)
hydrolyzed

(Zhang and
statistic
Tang, 2010)
 Ref Chemical composition Structure

(Soane et al., Alternate copolymer

2011) Mw=80 kDa

Multiblock
Structure
(Wilson et al.,
2013) Micellar controlled
polymerization
2 K<Mn<25 K

A tapered copolymer of vinyl acetate (VA) and acrylic acid (AA) neutralized with ammonia has
been patented (Caneba, 2010) as polymeric surfactant for EOR applications. Experiments of oil
recovery with such tapered VA-AA (containing a certain amount of random copolymer) give a
recovery of 17–41% OOIP. Hydrophobic acrylates (e.g. EA, BA) are proposed as substitutes of
the VA, being more resistant to hydrolysis.

Alternate copolymers of styrene and secondary amines proved to be good viscosifier agents and
showed pH-dependent emulsification ability, forming stable emulsions in basic conditions which
separate as the pH is decreased (Soane et al., 2011).

A process for EOR recently patented, claims the use of a 25% hydrolyzed PAM modified with
0.4% of a cationic hydrophobic monomer. In this formulation, the polymer is used in
combination with a very small amount of an anionic surfactant. It has been found that the
emulsifying ability of this mixture is much better than the one of the surfactant alone, even at a
surfactant concentration ten times higher (Favero and Gaillard 2010). The authors don’t give any
explanation for this behavior and define it “surprising”.

The polymer (Hough et al., 2010), a block copolymer of styrene, acrylic acid and ethyl acrylate
(notably, prepared via controlled radical polymerizations), has been claimed as system for EOR.
The viscosity of their aqueous solution is retained in the presence of high salt concentrations,
provided that a non-ionic surfactant is included in the formulation.

Beside these specific examples, patents covering a very broad range of amphiphilic copolymers
for EOR can be also found: a recent patent (Zhang and Tang, 2010) includes a broad range of
partially hydrolyzed acrylamide based polymers, containing charged or neutral hydrophobic
monomers, having IFT values included in the range 0.1–15 mN/m. Interestingly, the tested
polymers give very good performance in terms of recovered oil in flooding experiments, proving
to be much better than an analogous ordinary PAM with a higher viscosity.
The patent (Huff et al., 2008) by BASF includes a very general formulation for EOR consisting
of a mixture of a surfactant and a polymeric co-surfactant. The co-surfactants are comb,
multiblock or star copolymers build with hydrophobic units (essentially α-olefins) and
hydrophilic units (maleic anhydride, vinyl alcohol, (meth)acrylic acid, vinylpyrrolidone, allyl
alcohol, PEO, PPO).

Surprisingly, most of the examples found in the patent literature are quite recent. Before 2008,
the majority of patent literature concerning polymers for EOR includes mostly non-associative
water soluble polymers.

3.2. Biobased systems

For evident reasons, polymers obtained by natural sources have also attracted attention as
potential polymeric surfactants for EOR, looking for a cheap and green alternative to traditional
systems. A sulfonated fatty ester surfactant, obtained by esterification and sulfonation of non-
edible Jatropha oil (Elraies et al., 2010) has been free radically copolymerized with AM in order
to synthesize a polymeric surfactant for EOR (Elraies et al., 2011). The structure of such polymer
is not really defined, but is a cheap material, partly obtained from a renewable source, which
possess good viscosity and interfacial activity, making it a good candidate for EOR.

Hydrophobically modified polysaccharides can show some surface activity and have been
proposed for EOR applications (Desbrieres and Babak 2010). Their surface activities are
generally low, because the usually rigid structures don’t allow the rearrangement of the
hydrophobic parts at water/air interface, as demonstrated, for example, for a pullulan
hydrophobically modified fatty esters derivative 4–35% of substitution (Henni et al., 2005;
Henni-Silhadi et al., 2008). The same observation has been made for chitin (Desbrieres and
Babak, 2006) and pectin (Miralles-Houzelle et al., 2001) derivatives. In these latter cases, the
surface properties seem to be better when the hydrophobic group is introduced as counter ion to
the charged polysaccharide backbone, instead of covalently linked, while the rheological
behavior is unaffected.

The surface and interface properties of a carboxymethylcellulose derived polymeric surfactant

(Fig. 6) have been evaluated (Cao and Li 2002). As usually desired for EOR applications, the
IFT reaches ultralow values (10−2–10−3 mN/m) in alkaline conditions, either with a sample of
Daquing crude oil and with a mixture of alkanes. Interestingly, the IFT value is lowered in the
presence of NaOH even for acid-free alkanes, which excludes the possibility of the formation of
surfactants in situ by deprotonation of carboxylic acids that can possibly be already contained in
the oil. The effect of decreasing the IFT is attributed to the disassembly of aggregates (as
evidenced by DLS measurements), which allows rearrangement of the single polymer chains at
the interface.
 1. Download full-size image

Fig. 6. Structure of the polymer studied in Ref. Cao and Li (2002) and IFT values as function of
equivalent alkane carbon number (EACN). Adapted with permission.

4. Conclusions and outlook

From a theoretical point of view, the use of polymeric surfactants for chemical enhanced oil
recovery could represent a valid alternative to the commonly used systems, since they potentially
combine desired rheological and interfacial properties in only one component, while in general
mixtures of different chemicals are required. This would present the advantage to avoid
separation and loss of some components during the flooding processes or unwanted interactions
(Sheng, 2010). This potential is confirmed by the recent appearance in the patent literature of
examples of polymeric surfactants for EOR (see Section 3.1). On the other hand, in most cases
complex experimental procedures and expensive starting materials are required, which so far
greatly limited this approach. In order to really exploit the potential of polymeric surfactants for
EOR, the advantages should overcome the increased costs. Despite its academic interest, it is
unlikely that the use of very expensive monomers in the formulation of polymeric surfactants for
EOR (as the example in Ref. Zou et al. (2011)) would represent a cost-effective option. In our
opinion, a much more promising way is represented by the introduction of biopolymers and bio-
based monomers (see Section 3.2). The clear advantages are constituted by availability of
starting materials, sustainability and bio-compatibility. Again, the required chemical
modifications and synthesis still limit this approach, but we believe that in would be worth to put
some more effort in this direction.

The effectiveness of polymeric surfactants can be questioned on the basis of the fact that it is
very difficult, if not impossible, to achieve ultralow values of IFT (for polymeric surfactants,
typical values are found in the range 0.1–15 mN/m). This can be considered another aspect that
holds back the use of polymeric surfactants for EOR. Ultralow IFT values have always been
considered necessary in order to achieve sufficiently high values of capillary number and thus
significant recovery (Lake, 1989). Nonetheless, this could be a too simplistic assumption, as
recently shown by some experiments, where oil recovery using a SP formulation gave better
results for intermediate values of IFT, rather than for ultralow ones (Yu et al., 2010). In our
opinion, it can also be argued that measurements of surface and interfacial tension might not be
the most appropriate to evaluate the effectiveness of a polymeric surfactant for EOR, because
these parameters might become irrelevant in the time-scale of the process (it usually lasts for
years).

Unfortunately, a clear picture cannot emerge yet, since not many experiments aimed at directly
evaluating the performances of polymeric surfactants in oil recovery can be found in literature.
Recently, core flood experiments performed with a traditional PAM and a hydrophobically
substituted one, showed that the latter gives a better recovery than the former at the same
polymer concentration (Lai et al., 2013). However, the systems are not compared at the same
viscosity, so it is impossible to draw any conclusions regarding a possible role of IFT in the
process. Actually, the authors of the mentioned work don’t even consider the IFT as a relevant
parameter, but they focus their discussion on salt tolerance and thermal stability.

As a general observation, and quite paradoxically, even though many hydrophobically

substituted water soluble polymers (which are, at least in principle, polymeric surfactants) have
been studied and even patented as solution thickeners for EOR, their interfacial properties have
been rarely considered. Therefore, even if there are indications that they might perform better
than non-hydrophobic polymers, it has not been clarified if - and to which extent - the interfacial
behavior is important in determining the efficiency in oil recovery. Interestingly, it has been
recently proposed, based on flooding experiments in an artificial porous medium, that even
hydrolyzed PAM with no hydrophobic substitution could emulsify the oil during the flooding
process (Meybodi et al., 2011).

Some issues still remain, that strongly limit the possibility of using polymeric surfactants in
EOR. On one hand, the lack of clear indications that polymeric surfactants could really give
better performances than traditional polymeric mixtures, other conditions being equal. Studies
are still too sparse and not systematic, which makes any consistent investment in this direction
too risky. Therefore, an important milestone is to produce more experimental data to establish if
ultralow IFT vales are really necessary in order to improve oil recovery. On the other hand, the
costs of some of the starting materials can be very high and the complicated synthesis necessary
to obtain polymeric surfactant not suitable for production in large scale. The scale-up might
prove to be challenging especially for particular macromolecular architectures (such as block
copolymers). In this respect, the most promising approach, also from the point of view of
sustainability, seems to be the possibility to use monomers and materials from green feedstock.
We think that more efforts in this directions are surely desirable.

To face the problems related to the decreasing oil availability, more efforts from the scientific
community and the exploration of economically suitable sources and processes are required.

In general, efforts in several directions are still required before polymeric surfactants can be
really considered not only potential, but suitable systems for enhanced oil recovery.

References
Abrams, 1975
A. AbramsThe influence of fluid viscosity, interfacial tension, and flow velocity on
residual oil saturation left by waterflood
 SPE J. (1975), pp. 437-447
Abu-Sharkh et al., 2001
B.F. Abu-Sharkh, G.O. Yahaya, S.A. Ali, I.W. KaziSolution and interfacial behavior of
hydrophobically modified water-soluble block copolymers of acrylamide and N-
phenethylacrylamide
J. Appl. Polym. Sci., 82 (2001), pp. 467-476
Abu-Sharkh et al., 2003
B.F. Abu-Sharkh, G.O. Yahaya, S.A. Ali, E.Z. Hamad, I.M. Abu-ReeshViscosity
behavior and surface and interfacial activities of hydrophobically modified water-
soluble acrylamide/N-phenyl acrylamide block copolymers
J. Appl. Polym. Sci., 89 (2003), pp. 2290-2300
Adams et al., 2003
M.L. Adams, A. Lavasanifar, G.S. KwonAmphiphilic block copolymers for drug
delivery
J. Pharm. Sci., 92 (2003), pp. 1343-1355
Alexandridis, 1996
P. AlexandridisAmphiphilic copolymers and their applications
Curr. Opin. Colloid Interface Sci., 1 (1996), pp. 490-501
Al-Sabagh, 2000
A.M. Al-SabaghSurface activity and thermodynamic properties of water-soluble
polyester surfactants based on 1,3-dicarboxymethoxybenzene used for enhanced oil
recovery
Polym. Adv. Technol., 11 (2000), pp. 48-56
Al-Sabagh et al., 2003
A.M. Al-Sabagh, N.S. Ahmed, A.M. Nassar, M.M. GabrSynthesis and evaluation of
some polymeric surfactants for treating crude oil emulsions – Part I: treatment of
sandy soil polluted with crude oil by monomeric and polymeric surfactants
Colloids Surf. A, 216 (2003), pp. 9-19
Alvarado and Manrique, 2010
V. Alvarado, E. ManriqueEnhanced oil recovery: an update review
Energies, 3 (2010), pp. 1529-1575
Blanazs et al., 2009
A. Blanazs, S.P. Armes, A.J. RyanSelf-assembled block copolymer aggregates: from
micelles to vesicles and their biological applications
Macromol. Rapid Commun., 30 (2009), pp. 267-277
Busse et al., 2002
K. Busse, J. Kressler, D. van Eck, S. HoringSynthesis of amphiphilic block copolymers
based on tert-butyl methacrylate and 2-(N-methylperfluorobutanesulfonamido)ethyl
methacrylate and its behavior in water
Macromolecules, 35 (2002), pp. 178-184
Byham et al., 1980
Byham, D.E., Sheppard, E.W., Chen, C.S.H., 1980. United States of America Patent
4222881, 1980.
Caneba, 2010
Caneba, G., 2010. United States of America Patent 7691260.
Cao and Li, 2002
 Y. Cao, H.L. LiInterfacial activity of a novel family of polymeric surfactants
Eur. Polym. J., 38 (2002), pp. 1457-1463
Cayre et al., 2011
O.J. Cayre, N. Chagneux, S. BiggsStimulus responsive core-shell nanoparticles:
synthesis and applications of polymer based aqueous systems
Soft Matter, 7 (2011), pp. 2211-2234
Chen and Sheppard, 1981
Chen, C.S.H., Sheppard, E.W., 1981. United States of America Patent 4284517.
Chen and Sheppard, 1982
Chen, C.S.H., Sheppard, E.W., 1982. United States of America Patent 4317893.
Co et al., 2015
L. Co, Z. Zhang, Q. Ma, G. Watts, L. Zhao, P.J. Shuler, Y. TangEvaluation of
functionalized polymeric surfactants for EOR applications in the Illinois basin
J. Pet. Sci. Eng., 134 (2015), pp. 167-175
Crevecoeur et al., 1999
J.J. Crevecoeur, L. Nelissen, P.J. LemstraWater expandable polystyrene (WEPS)
(Part) 2. In-situ synthesis of (block)copolymer surfactants
Polymer, 40 (1999), pp. 3691-3696
Dai et al., 2008
S. Dai, P. Ravi, K.C. TampH-Responsive polymers: synthesis, properties and
applications
Soft Matter, 4 (2008), pp. 435-449
Desbrieres and Babak, 2006
J. Desbrieres, V.G. BabakInterfacial properties of amphiphilic natural polymer
systems based on derivatives of chitin
Polym. Int., 55 (2006), pp. 1177-1183
Desbrieres and Babak, 2010
J. Desbrieres, V. BabakInterfacial properties of chitin and chitosan based systems
Soft Matter, 6 (2010), pp. 2358-2363
de la Fuente et al., 2005
J.L. de la Fuente, M. Wilhelm, H.W. Spiess, E.L. Madruga, M. Fernandez-Garcia, M.L.
CerradaThermal, morphological and rheological characterization of poly(acrylic
acid-g-styrene) amphiphilic graft copolymers
Polymer (2005), p. 46
Dimitrov et al., 2007
I. Dimitrov, B. Trzebicka, A.H.E. Muller, A. Dworak, C.B. TsvetanovThermosensitive
water-soluble copolymers with doubly responsive reversibly interacting entities
Prog. Polym. Sci., 32 (2007), pp. 1275-1343
Durand and Marie, 2009
A. Durand, E. MarieMacromolecular surfactants for miniemulsion polymerization
Adv. Colloid Interface Sci., 150 (2009), pp. 90-105
Elraies et al., 2010
K.A. Elraies, I.M. Tan, M. Awang, I. SaaidThe synthesis and performance of sodium
methyl ester sulfonate for enhanced oil recovery
Pet. Sci. Technol., 28 (2010), pp. 1799-1806
Elraies et al., 2011
 K.A. Elraies, I.M. Tan, M.T. Fathaddin, A. Abo-JabalDevelopment of a new polymeric
surfactant for chemical enhanced oil recovery
Pet. Sci. Technol., 29 (2011), pp. 1521-1528
Evani, 1989
Evani, S., 1989. United States of America Patent 4814096.
Ezell and McCormick, 2007
R.G. Ezell, C.L. McCormickElectrolyte- and pH-responsive polyampholytes with
potential as viscosity-control agents in enhanced petroleum recovery
J. Appl. Polym. Sci., 104 (2007), pp. 2812-2821
Favero and Gaillard, 2010
Favero, C., Gaillard, N., 2010. United States of America Patent US 2010/0197529 A1.
Fischer et al., 2001
A. Fischer, A. Brembilla, P. LochonSynthesis of new amphiphilic cationic block
copolymers and study of their behaviour in aqueous medium as regards
hydrophobic microdomain formation
Polymer, 42 (2001), pp. 1441-1448
Garnier et al., 2006
S. Garnier, A. Laschewsky, J. StorsbergPolymeric surfactants: novel agents with
exceptional properties
Tenside Surfactants Deterg., 43 (2006), pp. 88-102
Ghosh et al., 2011
A. Ghosh, S. Yusa, H. Matsuoka, Y. SaruwatariNon-surface activity and micellization
behavior of cationic amphiphilic block copolymer synthesized by reversible
addition-fragmentation chain transfer process
Langmuir, 27 (2011), pp. 9237-9244
Gil and Hudson, 2004
E.S. Gil, S.M. HudsonStimuli-reponsive polymers and their bioconjugates
Prog. Polym. Sci., 29 (2004), pp. 1173-1222
Grace, 1982
H.P. GraceDispersion phenomena in high-viscosity immiscible fluid systems and
application of static mixers as dispersion devices in such systems
Chem. Eng. Commun., 14 (1982), p. 225
Green, 1998
Green, D.W., Willhite, G.P., Enhanced Oil Recovery 1998, SPE Publications,
Richardson, Texas, 978-1-55563-077-5
Henni et al., 2005
W. Henni, M. Deyme, M. Stchakovsky, D. LeCerf, L. Picton, W. RosilioAggregation of
hydrophobically modified polysaccharides in solution and at the air-water interface
J. Colloid Interface Sci., 281 (2005), pp. 316-324
Henni-Silhadi et al., 2008
W. Henni-Silhadi, M. Deyme, M.R. de Hoyos, D. Le Cerf, L. Picton, V.
RosilioInfluence of alkyl chains length on the conformation and solubilization
properties of amphiphilic carboxymethylpullulans
Colloid Polym. Sci., 286 (2008), pp. 1299-1305
Hietala et al., 2007
 S. Hietala, P. Mononen, S. Strandman, P. Jarvi, M. Torkkeli, K. Jankova, S. Hvilsted, H.
TenhuSynthesis and rheological properties of an associative star polymer in aqueous
solutions
Polymer (2007), p. 48
Hirasaki et al., 2011
G.J. Hirasaki, C.A. Miller, M. PuertoRecent advances in surfactant EOR
SPE J., 16 (2011), pp. 889-907
Hough et al., 2010
Hough, L.A., Lizarraga, G.M., Adam, H., Castaing, J., Kesavan, S., 2010. United States
of America Patent 7789160.
Huff et al., 2008
Huff, J., Oetter, G., Kuhnle, A., Petrovic, S., Guzmann, M., Munster, I., Brodt, G., 2008.
United States of America Patent US2008/0194435 A1.
Huff et al., 2011
Huff, J., Oetter, G., Kuhnle, G., Petrovic, G., Guzmann, M., Munster, I., Brodt, G., 2011.
United States of America Patent 8053396.
Iddon et al., 2004
P. Iddon, K. Robinson, S. ArmesPolymerization of sodium 4-styrenesulfonate via
atom transfer radical polymerization in protic media
Polymer, 45 (2004), pp. 759-768
Iglauer et al., 2010
S. Iglauer, Y. Wu, P. Shuler, Y. Tang, W.A. Goddard IIINew surfactant classes for
enhanced oil recovery and their tertiary oil recovery potential
J. Pet. Sci. Technol., 71 (2010), p. 23
Jacquin et al., 2010
M. Jacquin, P. Muller, H. Cottet, O. TheodolySelf-assembly of charged amphiphilic
diblock copolymers with insoluble blocks of decreasing hydrophobicity: from
kinetically frozen colloids to macrosurfactants
Langmuir, 26 (2010), pp. 18681-18693
Jacquin et al., 2007
M. Jacquin, P. Muller, H. Cottet, R. Crooks, O. TheodolyControlling the melting of
kinetically frozen poly(butyl acrylate-b-acrylic acid) micelles via addition of
surfactant
Langmuir, 23 (2007), pp. 9939-9948
Jain and Bates, 2003
S. Jain, F. BatesOn the origins of morphological complexity in block copolymer
surfactants
Science, 300 (2003), pp. 460-464
Jiang et al., 2009
H. Jiang, P. Taranekar, J.R. Reynolds, K.S. SchanzeConjugated polyelectrolytes:
synthesis, photophysics, and applications
Angew. Chem. Int. Ed., 48 (2009), pp. 4300-4316
Kaewsaiha et al., 2005
P. Kaewsaiha, K. Matsumoto, H. MatsuokaNon-surface activity and micellization of
ionic amphiphilic diblock copolymers in water. Hydrophobic chain length
dependence and salt effect on surface activity and the critical micelle concentration
 Langmuir, 21 (2005), pp. 9938-9945
Kudaibergenov et al., 2006
S. Kudaibergenov, W. Jaeger, A. LaschewskyPolymeric betaines: synthesis,
characterization, and application
Adv. Polym. Sci., 201 (2006), pp. 157-224
Kudaibergenov, 1999
S.E. KudaibergenovRecent advances in the study of synthetic polyampholytes in
solutions
Adv. Polym. Sci., 144 (1999), p. 115
Kudaibergenov and Ciferri, 2007
S.E. Kudaibergenov, A. CiferriNatural and synthetic polyampholytes, 2(a) functions
and applications
Macromol. Rapid Commun., 28 (2007), pp. 1969-1986
Kwon and Kataoka, 1995
G.S. Kwon, K. KataokaBlock-copolymer micelles as long-circulating drug vehicles
Adv. Drug Deliv. Rev., 16 (1995), pp. 295-309
Lai et al., 2013
N. Lai, W. Dong, Z. Ye, J. Dong, X. Qin, W. Chen, K. ChenA water-soluble acrylamide
hydrophobically associating polymer: synthesis, characterization, and properties as
EOR chemical
J. Appl. Polym. Sci., 129 (2013), pp. 1888-1896
Lake, 1989
L.W. LakeEnhanced Oil Recovery
Prentice Hall,, New Jersey (1989), p. 555
Liu et al., 2007
R.C.W. Liu, A. Pallier, M. Brestaz, N. Pantoustier, C. TribetImpact of polymer micro
structure on the self-assembly of amphiphilic polymers in aqueous solutions
Macromolecules (2007), p. 40
Maia et al., 2009
A.M.S. Maia, R. Borsali, R.C. BalabanComparison between a polyacrylamide and a
hydrophobically modified polyacrylamide flood in a sandstone core
Mater. Sci. Eng. C – Biomim. Supramol. Syst., 29 (2009), pp. 505-509
Matsuoka et al., 2004
H. Matsuoka, S. Maeda, P. Kaewsaiha, K. MatsumotoMicellization of non-surface-
active diblock copolymers in water. Special characteristics of poly(styrene)-block-
poly(styrenesulfonate)
Langmuir, 20 (2004), pp. 7412-7421
McCormick et al., 2006
C.L. McCormick, S.E. Kirkland, A.W. YorkSynthetic routes to stimuli-responsive
micelles, vesicles, and surfaces via controlled/living radical polymerization
J. Macromol. Sci., Part C: Polym. Rev., 46 (2006), p. 421
Meybodi et al., 2011
H.E. Meybodi, R. Kharrat, X. WangStudy of microscopic and macroscopic
displacement behaviors of polymer solution in water-wet and oil-wet media
Transp. Porous Media, 89 (2011), pp. 97-120
Miralles-Houzelle et al., 2001
 M.C. Miralles-Houzelle, P. Hubert, E. DellacherieHydrophobic alkyl chains-pectin
conjugates. Comparative study of some physicochemical properties in relation to
covalent coupling vs ionic association
Langmuir, 17 (2001), pp. 1384-1391
Nayak et al., 2011
R.R. Nayak, T. Yamada, H. MatsuokaNon-surface activity of cationic amphiphilic
diblock copolymers
Mater. Sci. Eng., 24 (2011), p. 1
Nazar et al., 2011
M.F. Nazar, S.S. Shah, M.A. KhosaMicroemulsions in enhanced oil recovery: a
review
Pet. Sci. Technol., 29 (2011), pp. 1353-1365
Olajire, 2014
A.A. OlajireReview of ASP EOR (alkaline surfactant polymer enhanced oil
recovery) technology in the petroleum industry: prospects and challenges
Energy, 77 (2014), pp. 963-982
Popot et al., 2003
J.L. Popot, E.A. Berry, D. Charvolin, C. Creuzenet, C. Ebel, D.M. Engelman, M.
Flotenmeyer, F. Giusti, Y. Gohon, P. Herve, Q. Hong, J.H. Lakey, K. Leonard, H.A.
Shuman, P. Timmins, D.E. Warschawski, F. Zito, M. Zoonens, B. Pucci, C.
TribetAmphipols: polymeric surfactants for membrane biology research
Cell. Mol. Life Sci., 60 (2003), pp. 1559-1574
Qin et al., 1994
A.W. Qin, M.M. Tian, C. Ramireddy, S.E. Webber, P. Munk, Z. TuzarPolystyrene
poly(methacrylic acid) block-copolymer micelles
Macromolecules, 27 (1994), pp. 120-126
Raffa et al., 2014
P. Raffa, M.C.A. Stuart, A.A. Broekhuis, F. PicchioniThe effect of hydrophilic and
hydrophobic block length on the rheology of amphiphilic diblock Polystyrene-b-
Poly(sodium methacrylate) copolymers prepared by ATRP
J. Colloid Interface Sci., 428 (2014), pp. 152-161
Raffa et al., 2015
P. Raffa, D.A.Z. Wever, F. Picchioni, A.A. BroekhuisPolymeric surfactants: synthesis,
properties, and links to applications
Chem. Rev., 115 (2015), pp. 8504-8563
Raffa et al., 2013
P. Raffa, P. Brandenburg, D.A.Z. Wever, A.A. Broekhuis, F. PicchioniPolystyrene-
poly(sodium methacrylate) amphiphilic block copolymers by ATRP: effect of
structure, pH, and ionic strength on rheology of aqueous solutions
Macromolecules, 46 (2013), pp. 7106-7111
Raffa et al., 2016
P. Raffa, A.A. Broekhuis, F. PicchioniAmphiphilic copolymers based on PEG-acrylate
as surface active water viscosifiers: towards new potential systems for enhanced oil
recovery
J. Appl. Polym. Sci., 133 (2016), p. 44100
Rashidi et al., 2010
 M. Rashidi, A.M. Blokhus, A. SkaugeViscosity study of salt tolerant polymers
J. Appl. Polym. Sci., 117 (2010), pp. 1551-1557
Reed and Healy, 1977
Reed, R.L., Healy, R.N., 1977. Some Physicochemical Aspects of Microemulsion
Flooding: A Review. In: Shah, D.O., Schechter, R.S. (Eds.), Academic Press, New York,
pp. 383–437.
Rodriguez-Hernandez et al., 2005
J. Rodriguez-Hernandez, F. Checot, Y. Gnanou, S. LecommandouxToward 'smart’
nano-objects by self-assembly of block copolymers in solution
Prog. Polym. Sci., 30 (2005), pp. 691-724
Savu and Sierakowski, 2010
Savu, P.M., Sierakowski, M.J., 2010. United States of America Patent US 2010/0044050
A1.
Shaikh et al., 1999
S. Shaikh, S.A. Ali, E.Z. Hamad, B.F. Abu-SharkhSynthesis and solution properties of
poly(acrylamide-styrene) block copolymers with high hydrophobic content
Polym. Eng. Sci., 39 (1999), pp. 1962-1968
Sheng, 2010
J.J. ShengModern Chemical Enhanced Oil Recovery: Theory and Practice
Elsevier, (2010), p. 648
Soane et al., 2011
Soane, D., Mahoney, R.P., Portilla, R.C., 2011. United States of America Patent US
2011/0100402 A1.
Sun et al., 2010
J. Sun, X. Xu, J. Wang, W. Zhang, H. Yang, X. Jing, X. ShiSynthesis and
emulsification properties of an amphiphilic polymer for enhanced oil recovery
J. Dispers. Sci. Technol., 31 (2010), pp. 931-935
Tadros, 2009
T. TadrosPolymeric surfactants in disperse systems
Adv. Colloid Interface Sci., 147–48 (2009), pp. 281-299
Taubert et al., 2004
A. Taubert, A. Napoli, W. MeierSelf-assembly of reactive amphiphilic block
copolymers as mimetics for biological membranes
Curr. Opin. Chem. Biol., 8 (2004), pp. 598-603
Taylor and Nasr-El-Din, 1998
K.C. Taylor, H.A. Nasr-El-DinWater-soluble hydrophobically associating polymers
for improved oil recovery: a literature review
J. Pet. Sci. Technol., 19 (1998), pp. 265-280
Theodoly et al., 2009
O. Theodoly, M. Jacquin, P. Muller, S. ChhunAdsorption kinetics of amphiphilic
diblock copolymers: from kinetically frozen colloids to macrosurfactants
Langmuir, 25 (2009), pp. 781-793
Thomas, 2008
S. ThomasEnhanced oil recovery – an overview
Oil Gas Sci. Technol., 63 (2008), pp. 9-19
Torchilin, 2001
 V.P. TorchilinStructure and design of polymeric surfactant-based drug delivery
systems
J. Control. Release, 73 (2001), pp. 137-172
van de Kraats and Sawyer, 1976
van de Kraats, E.J., Sawyer, M.J., 1976. United States of America Patent 3984333.
Walstra, 1993
P. WalstraPrinciples of emulsion formation
Chem. Eng. Sci., 48 (1993), pp. 333-349
Wever et al., 2011
D.A.Z. Wever, F. Picchioni, A.A. BroekhuisPolymers for enhanced oil recovery: a
paradigm for structure-property relationship in aqueous solution
Prog. Polym. Sci., 36 (2011), p. 1558
Wever et al., 2013b
D.A.Z. Wever, F. Picchioni, A.A. BroekhuisComblike polyacrylamides as flooding
agent in enhanced oil recovery
Ind. Eng. Chem. Res., 52 (2013), pp. 16352-16363
Wever et al., 2013d
D.A.Z. Wever, F. Picchioni, A.A. BroekhuisBranched polyacrylamides: synthesis and
effect of molecular architecture on solution rheology
Eur. Polym. J., 49 (2013), pp. 3289-3301
Wever et al., 2012
D.A.Z. Wever, P. Raffa, F. Picchioni, A.A. BroekhuisAcrylamide homopolymers and
acrylamide-N-isopropylacrylamide block copolymers by atomic transfer radical
polymerization in water
Macromolecules, 45 (2012), pp. 4040-4045
Wever et al., 2013a
D.A.Z. Wever, E. Riemsma, F. Picchioni, A.A. BroekhuisComb-like thermoresponsive
polymeric materials: synthesis and effect of macromolecular structure on solution
properties
Polymer, 54 (2013), pp. 5456-5466
Wever et al., 2014
D.A.Z. Wever, G. Ramalho, F. Picchioni, A.A. BroekhuisAcrylamide-b-N-
Isopropylacrylamide block copolymers: synthesis by atomic transfer radical
polymerization in water and the effect of the hydrophilic–hydrophobic ratio on the
solution properties
J. Appl. Polym. Sci. (2014), p. 131
Wever et al., 2013c
D.A.Z. Wever, L.M. Polgar, M.C.A. Stuart, F. Picchioni, A.A. BroekhuisPolymer
molecular architecture as a tool for controlling the rheological properties of aqueous
polyacrylamide solutions for enhanced oil recovery
Ind. Eng. Chem. Res., 52 (2013), pp. 16993-17005
Wilson et al., 2013
Wilson, J., Destarac, M., Cadix, A., 2013. World Patent WO2013060741 A1.
Winnik and Yekta, 1997
M.A. Winnik, A. YektaAssociative polymers in aqueous solution
Curr. Opin. Colloid Interface Sci., 2 (1997), pp. 424-436
Yahaya et al., 2001
G.O. Yahaya, A.A. Ahdab, S.A. Ali, B.F. Abu-Sharkh, E.Z. HamadSolution behavior of
hydrophobically associating water-soluble block copolymers of acrylamide and N-
benzylacrylamide
Polymer, 42 (2001), pp. 3363-3372
Yahya and Hamad, 1995
G.O. Yahya, E.Z. HamadSolution behavior of sodium maleate/1-alkene copolymers
Polymer, 36 (1995), pp. 3705-3710
Yahya et al., 1996
G.O. Yahya, S.K.A. Ali, E.Z. HamadSurface and interfacial activities of
hydrophobically modified poly(vinyl alcohol) (PVA)
Polymer, 37 (1996), pp. 1183-1188
York et al., 2008
A.W. York, S.E. Kirkland, C.L. McCormickAdvances in the synthesis of amphiphilic
block copolymers via RAFT polymerization: Stimuli-responsive drug and gene
delivery
Adv. Drug Deliv. Rev., 60 (2008), pp. 1018-1036
Yu et al., 2008
F. Yu, W. Fan, S. Li, G. Nan, X. Chen, Y. DuanStudy on synthesis and applied
performance of petroleum sulfonate for enhanced oil recovery
J. Dispers. Sci. Technol., 29 (2008), pp. 975-984
Yu et al., 2010
Q. Yu, H. Jiang, C. ZhaoStudy of interfacial tension between oil and surfactant
polymer flooding
Pet. Sci. Technol., 28 (2010), pp. 1846-1854
Zaroslov et al., 2005
Y.D. Zaroslov, G. Fytas, M. Pitsikalis, N. Hadjichristidis, O.E. Philippova, A.R.
KhokhlovClusters of optimum size formed by hydrophobically associating
polyelectrolyte in homogeneous solutions and in supernatant phase in equilibrium
with macroscopic physical gel
Macromol. Chem. Phys., 206 (2005), p. 173
Zhang et al., 2010
H. Zhang, M. Dong, S. ZhaoWhich one is more important in chemical flooding for
enhanced court heavy oil recovery, lowering interfacial tension or reducing water
mobility?
Energy Fuels, 24 (2010), pp. 1829-1836
Zhang and Tang, 2010
Zhang, R., Tang, Y., 2010. United States of America Patent US 2010/0029880 A1.
Zhao et al., 2009
Y. Zhao, J. Zhou, X. Xu, W. Liu, J. Zhang, M. Fan, J. WangSynthesis and
characterization of a series of modified polyacrylamide
Colloid Polym. Sci., 287 (2009), pp. 237-241
Zhou et al., 2009
J. Zhou, L. Wang, J. MaRecent research progress in the synthesis and properties of
amphiphilic block co-polymers and their applications in emulsion polymerization
Des. Monomer Polym., 12 (2009), pp. 19-41
Zhou and Yan, 2009
Y. Zhou, D. YanSupramolecular self-assembly of amphiphilic hyperbranched
polymers at all scales and dimensions: progress, characteristics and perspectives
Chem. Commun., 10 (2009), pp. 1172-1188
Zou et al., 2011
C. Zou, H. Wu, L. Ma, Y. LeiPreparation and application of a series of novel anionic
acrylamide polymers with cyclodextrin sides
J. Appl. Polym. Sci., 119 (2011), pp. 953-961
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