Review

pubs.acs.org/CR

Polymeric Surfactants: Synthesis, Properties, and Links to

Applications
Patrizio Raffa,†,‡ Diego Armando Zakarias Wever,†,‡ Francesco Picchioni,† and Antonius A. Broekhuis*,†
†
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
Abbreviations 8550
References 8551

1. INTRODUCTION
It is well-known that surfactants are molecules able to modify the
surface properties of the liquid in which they are introduced
(usually water). The simultaneous presence of both hydrophilic
and hydrophobic parts in the same molecule has been recognized
as the key feature of these systems, which is responsible for their
CONTENTS characteristic properties in solution. These include adsorption at
1. Introduction 8504 interfaces and self-assembly into a variety of micellar aggregates
2. Classification of Polymeric Surfactants 8506 above a critical value of concentration, called critical micelle
2.1. Polysoaps 8506 concentration (CMC). Indeed, the term “solution” in this
2.2. Macrosurfactants 8507 respect has to be used carefully: it ceases to be correct above
2.3. Complex Architectures 8507 CMC, since the surfactant is no longer homogeneously dispersed
3. Synthetic Methods 8512 at a molecular level into the water phase.
3.1. Synthesis of Macrosurfactants 8512 By structural analogy with their low molecular weight
3.1.1. Polyacrylic and Methacrylic Acid Blocks 8512 counterparts, macromolecules containing both hydrophilic and
3.1.2. Aromatic Sulfonate Blocks 8516 hydrophobic parts can be generally referred to as polymeric
3.1.3. Polyvinylpyridines and Quaternized Aryl- surfactants. This general definition includes most of the
amines Blocks 8516 macromolecular systems that in the literature are also described
3.1.4. Poly(ethylene glycol)/Poly(ethylene as amphiphilic polymers, micellar polymers, hydrophobically
oxide) Blocks 8518 modified water-soluble polymers, associative polymers, and
3.1.5. Alkylaminoacrylate Blocks 8523 related terms. If the hydrophilic part is charged, they can fall
3.1.6. Other Water-Soluble Acrylate Blocks 8527 under the categories of polyelectrolytes or polyampholytes (in
3.2. Synthesis of Polysoaps 8527 the latter case, when the hydrophilic part contains simultaneously
3.2.1. Polyacrylamides and Related 8529 negative and positive charges). Compared to low-molecular-
3.2.2. Hydrophobically Modified Polysacchar- weight surfactants, polymeric ones offer a much higher structural
ides 8529 complexity (for example, in the number and distribution of
3.3. Synthesis of Complex Polymeric Surfactants 8530 hydrophilic and hydrophobic moieties along the chain), which
4. Properties of Polymeric Surfactants 8533 can result in very different behavior.
4.1. Surface Properties 8533 It is interesting to note that several natural polymers are, in
4.1.1. Macrosurfactants 8535 fact, polymeric surfactants.1,2 The most notable example is
4.1.2. Polysoaps 8539 represented by proteins. Even though they are generally not
4.2. Rheology of Macrosurfactants 8542 considered from this point of view, in many cases proteins are
5. Links between Properties and Applications of found in natural systems as emulsion stabilizers (e.g., casein in
Polymeric Surfactants 8545 milk). The other main class of naturally occurring polymeric
5.1. Emulsion Stabilization 8545 surfactants is polysaccharides. Emulsan (a lipopolysaccharide)
5.2. Coatings 8546 and chitosan are notable examples.3 It is usually very difficult to
5.3. Oil Recovery 8547 isolate polymeric surfactants from natural sources, and their
6. Conclusions 8548 structures and compositions can vary depending on the source;
Author Information 8549 therefore, most of the systems studied and reported in the
Corresponding Author 8549 literature are synthetic.
Notes 8549
Biographies 8549 Received: March 4, 2014
Acknowledgments 8550 Published: July 16, 2015

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Figure 1. Schematic representation of the different behavior displayed in solution and at the air/water interface by polysoaps (left) and macrosurfactants
(center). Very few data points are available about complex architectures (right).
As a common feature, polymeric surfactants show interesting
association phenomena in selective solvents, which results in
peculiar rheological behavior and the formation of self-assembled
structures. For these reasons, they have received increasing
attention in the last few decades, in particular for their actual and
potential applications in several fields including (mini)emulsion
polymerizations, coatings, biotechnology, nanotechnology,
medicine, pharmacology, cosmetics, agriculture, water purifica-
tion, electronic, optoelectronic, and enhanced oil recovery.4−31
Also of great interest from the applicative point of view is the
possibility of introducing responsive behavior to external
parameters (such as pH, temperature, electrolytes concentration,
and UV irradiation), which is at the basis of the design of smart
materials.32−40
The case of Pluronic systems (block copolymers of PEO and
PPO) is paradigmatic of the evolution of polymeric surfactants.
First commercialized (by BASF) as industrial detergents, they
found afterward important applications in medicine as drug
carriers. In recent years, the interest in these polymers increased
even more, as they showed potential in treatment of cancer.41
In addition to their great potential for applications, these
systems still represent an exciting challenge from a more
fundamental point of view. As anticipated, their macromolecular
nature affords a range of architectures, length scales, time scales,
and levels of interactions much wider than those offered by small
amphiphilic molecules. At the same time, such diversity poses
great challenges in the characterization and understanding of the
solution and surface properties of large amphiphiles.
Especially after the development of controlled radical
polymerization methods, such as NMP, ATRP, and RAFT (in
the late 1990s), the number of available compositions and
structures has increased enormously. These synthetic techniques
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have provided a really solid basis to better study the effect of
composition and molecular architecture on the properties of
amphiphilic copolymers, given the possibility to prepare well-
defined structures with almost no limitations in geometry and
chemistry. In recent decades the synthetic strategies for polymers
have reached their maturity. It is now possible to build
macromolecular structures with tailored characteristics; molec-
ular weights, compositions, architectures, and molecular weight
distributions can be controlled almost without limitations. This
allows in turn studying systematically the structure−properties
relationships and ultimately selecting the structures more
suitable for a desired application.
The influence of the different architecture on the properties of
amphiphilic polymers has raised interest for decades. It is well-
established that a polysoap (polymer of an intrinsically
amphiphilic monomer or a random copolymer of hydrophilic
and hydrophobic monomers) can undergo intramolecular
aggregation in water. Block copolymers with hydrophilic and
hydrophobic blocks, on the other hand, will mostly give
intermolecular aggregation (Figure 1). Also the arrangement at
the water/air interface can be sensibly different. From this,
completely different properties can be expected and are, in fact,
observed. Little is known about the association behavior of
amphiphilic polymers characterized by complex architectures.
The main purposes of the present review are (1) to provide a
general overview of the synthetic strategies adoptable for the
synthesis of polymeric surfactants, depending on the desired
moleculare architecture; (2) to summarize the available
information about the structure−properties relationship, espe-
cially concerning surface activity and rheology; and (3) to
provide a link between properties and final applications (actual or
potential).
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Figure 2. Classification of polymeric surfactants
Against this backdrop, particular attention will be given to the
application of these materials in enhanced oil recovery. Besides
the coupling with the current research activities in our group,
EOR provides a paridigmatic example for which all aspects of
polymeric surfactant properties (in turn related to the chemical
structure) can be conveniently discussed. Furthermore, it
provides a relevant topic of investigation (at both academic
and industrial levels) also in relation to the current suistainability
climate and the efficient use of energy sources.
2. CLASSIFICATION OF POLYMERIC SURFACTANTS
In general, polymeric surfactants are divided, from a structural
point of view, into two main classes, depending on the relative
distribution of hydrophilic and lipophilic parts. Macromolecules
constituted by repeating units of intrinsically amphiphilic
monomers or oligomers are generally referred to as “polysoaps”,
whereas polymers in which there is a neat separation between the
two parts are called “macrosurfactants”.4,26,42 Polysoaps are
defined as polymers that contain a surfactant-like entity in the
polymer repeating unit.43 This situation can be present in
polymers of polymerizable surfactants (both homopolymers and
random copolymers in which at least one monomer is a
surfactant), as well as in statistic or alternating copolymers of
hydrophilic and hydrophobic monomers. Also segmented
multiblock polymers are preferentially included in the class of
polysoaps.4
The second class includes essentially amphiphilic linear,
branched, and grafted block copolymers in which there is a
clear spatial segregation between hydrophilic and hydrophobic
parts.21 Amphiphilic ABA or ABC triblock copolymers usually
belong to the class of macrosurfactants.26
It is useful to treat polysoaps and macrosurfactants separately,
because their structural differences lead in a quite general way to
a completely dissimilar associative behavior in water. At low
concentrations in water, polysoaps will give essentially intra-
molecular hydrophobic association,4 forming unimeric micelles
(in fact, this characteristic has also been used as an alternative
definition of polysoaps44); intermolecular aggregation starts to
appear at higher concentrations.45 The prevalence of intra-
molecular over intermolecular association is dependent on
several structural factors, including the relative amount and
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distribution of hydrophobic and hydrophilic parts, which will be
discussed in more detail later.46,47
Macrosurfactants, on the other hand, seem to exclusively give
intermolecular aggregation in water solutions, even in conditions
of extreme dilution.21 The behavior of polysoaps and macro-
surfactants in solution is schematically illustrated in Figure 1 and
will be discussed in detail in section 4.
It is evident that this has great consequences on rheological
properties and surface activity of polymeric surfactants.
However, it has to be pointed out that the balance between
intramolecular and intermolecular aggregation is affected by
several factors such as concentration, temperature, pH, and ionic
strength. Consequently, the same polymeric surfactant can give
both kinds of aggregation depending on the employed
conditions (which is the basic concept of the stimuli-responsive
behavior). Moreover, from the point of view of molecular
structures, several intermediate situations can be found,
especially in complex molecular architectures such as multiblock,
star block, multibranched, and dendrimeric polymers. In such
cases the distinction is not trivial and the aggregation behavior is
not easy to infer. Also, gradient amphiphilic copolymers and
block copolymers containing a polysoap block represent special
cases that cannot be clearly classified. Because the ability to form
intermolecular aggregates with tunable structure and stability is
undoubtedly the most attractive feature of polymeric surfactants,
recently the research has been focused on macrosurfactants. This
is especially related to the establishment of controlled radical
polymerization methods (NMP, ATRP, and RAFT) as very
versatile alternatives to anionic polymerizations for the synthesis
of block copolymers. The availability of synthetic procedures,
which allow for obtaining complex architectures in a very precise
and controlled fashion, has also favored the increase of the
interest in these kinds of amphiphilic polymers.17,48−50 For these
reasons, they can be considered as a different and new class of
polymeric surfactants (Figure 2).
2.1. Polysoaps
As anticipated, we will consider here polymers for which
hydrophobic and hydrophilic parts are scattered all over the
polymer backbone. The term “polysoap” was coined for these
polymers by Strauss, who pioneered the research on their
aggregation properties in the 1950s.51−53 As they usually bear
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Figure 3. Structures of complex polymeric surfactants. A, B, and C indicate different monomers, where at least one is hydrophobic and at least one is
hydrophilic. Adapted with permission from ref 21. Copyright 2003 Elsevier.
charged functional groups, these polymeric surfactants are often
referred to as hydrophobic or hydrophobically modified
polyelectrolytes,54,55 polyampholytes (when both anionic and
cationic monomers are present),56,57 or polyzwitterions/
zwitterionic polymers (when both cationic and anion groups
are present in the same monomer).58 Most of the polymers
utilized or designed for EOR (taken here as an example of a
relevant application field) can be included in this class. In this
regard, the most popular and studied systems are hydrophobi-
cally modified polyacrylamides, polyacrylates, and polysacchar-
ides. A very extensive review by Laschewsky4 gives an overview of
all the possible structures and properties of polysoaps that can be
found in the literature. Despite being the most important feature
of polysoaps, their surface activity has been rarely studied.4
2.2. Macrosurfactants
Amphiphilic diblock copolymers are the most important
polymers included in the class of macrosurfactants. They have
received great interest, especially for their ability to form micellar
aggregates exhibiting stimuli-responsive behavior in aqueous
solutions, which allows for preparing smart materials for several
applications. A number of reviews concerning synthesis,
micellization, emulsions stabilization, and stimuli-responsive
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behavior of amphiphilic block copolymers appeared in recent
literature.21−24,26,27,37−39,42,54,59−66
Basically, each polymer constituted by a water-insoluble block
and a water-soluble (charged or neutral) one can be included in
this class. Aside from permanently hydrophobic−hydrophilic
block copolymers, an increasing number of polymers with
tunable hydrophilicity of one or both blocks has been appearing
in the literature. These systems usually show pH- or temperature-
dependent micellization and surface activity. When both blocks
present switchable hydrophilicity, these polymers are often
referred to as “schizophrenic”.20,39,67−71
2.3. Complex Architectures
With the synthetic techniques available today, the only
limitations in the preparation of polymeric surfactants with
complex architectures are the interests and the imagination of the
researchers. In Figure 3 the structures of complex polymeric
surfactants, as summarized by Riess in 2003, are depicted.21
Despite the large number of synthesized structures, the study of
surface properties of such polymers is limited to a few cases,
which will be analyzed in the following sections.
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Table 1. List of Amphiphilic Block Copolymers Based on PAA and PMAA

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Table 1. continued

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Table 1. continued

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Table 1. continued

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Table 1. continued
3. SYNTHETIC METHODS
Here we will review the synthetic methods used to prepare
amphiphilic polymers whose surface activity in water has been
evaluated by direct measurement of surface and/or interface
tension, determination of critical micelle concentration (CMC,
often referred to as critical aggregation concentration or CAC),
and/or study of emulsions and latexes stability and related
systems.
The most common hydrophobic blocks are based on
polystyrene, polyacrylates, polyolefin, or nonwater-soluble
polyethers. Hydrophilic blocks are made of either negatively or
positively charged monomers, such as vinylic or acrylic
monomers bearing sulfonated, carboxylic, or amino groups, or
neutral blocks, which are essentially poly(ethylene glycol) (PEG)
moieties or hydrosoluble acrylates such as 2-hydroxyethyl
methacrylate (HEMA) or PEGylated acrylic monomers.
From the late 1990s, controlled living radical polymerization
methods such as atom transfer radical polymerization (ATRP),72
reversible addition-fragmentation chain transfer polymerization
(RAFT),73 and nitroxide-mediated polymerization (NMP)74,75
are becoming the synthetic approach of choice to produce
amphiphilic block copolymers with well-defined structure and
very narrow molecular weight distribution. However, there are
still some limitations related to functional groups tolerance that
often lead to the necessity of using protective or masked groups
that have to be subsequently removed or modified via additional
postpolymerization transformations. The advantage of these
methods is in the excellent control that can be achieved over
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composition and molecular weight distribution of the synthe-
sized polymer. Side reactions, such as chain termination by
disproportionation or chain transfer processes, are in most cases
completely suppressed. Ionic living polymerizationespecially
anionic76has always been the preferred way of synthesizing
well-defined amphiphilic block copolymers and is still largely
used.
Conventional free-radical polymerizations are also used, but
control over structure and molecular weight distribution is
generally poor. As a consequence of the development of versatile
controlled/living polymerizations, very few examples of synthesis
of amphiphilic block polymers via free radical polymerization are
found in the recent literature.
The approach for the synthesis of amphiphilic polymers is
often dependent on the nature of the hydrophilic block. We will
discuss and compare here the most used strategies for the
synthesis of amphiphilic copolymers, depending on the nature of
the hydrophilic part.
3.1. Synthesis of Macrosurfactants
3.1.1. Polyacrylic and Methacrylic Acid Blocks. Amphi-
philic polymers containing a polycarboxylate block show
interesting properties. In particular, the hydrophilicity of the
polyacid block is strongly dependent on the degree of
protonation of the carboxylic moieties and thus on the solution
pH. They are more frequently found as hydrophilic partners, but
their ability to form micelles in acidic conditions acting as
hydrophobic block in water has been also demonstrated.77
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The synthesis of block copolymers containing acrylic or
methacrylic acid is challenging because of the noncompatibility
of the free carboxylic group with most of the controlled
polymerization strategies (with RAFT being the only notable
exception).78−80 The general approach in those cases in which
the acid is not directly polymerizable consists of utilizing the
corresponding tert-butyl ester as monomer. This can be easily
converted into the free acid by postpolymerization reactions,
such as thermolysis, catalytic cleavage, or hydrolysis in both
acidic and basic conditions. This strategy also circumvents the
problem of finding a proper solvent for both the hydrophilic and
the hydrophobic partners, which is normally not trivial.
The precursor of choice for these systems is poly(tert-butyl
(meth)acrylate), which can be easily hydrolyzed into poly-
(meth)acrylic acid by the deprotection reaction with acids.
Typical conditions are hydrochloric acid in refluxing dioxane/
water,77,81−85 trifluoroacetic acid in dichloromethane,86−90 and
p-toluenesulfonic acid in refluxing toluene.91−94 The hydrolysis is
usually complete and very selective, especially in the case of TFA,
which is conducted in mild conditions, whereas for the HCl/
dioxane system a partial hydrolysis of the other sensitive groups
seems to occur, for example, the butyl ester in the case of PBA-
containing copolymers.95 Although less frequently, the tert-butyl
group can also be eliminated by thermal decomposition.96 A list
of relevant examples of block copolymers containing PAA or
PMAA is provided in Table 1.
Atom Transfer Radical Polymerization. Atom transfer radical
polymerization (ATRP) is increasingly used for the synthesis of
amphiphilic polymer containing a carboxylic acid as the repeating
unit in the hydrophilic block. As anticipated, the direct ATRP of a
free-carboxyl group containing monomer has been proven not
successful because of poisoning effects on the copper (II) species
formed in the reaction media.97 Ashford and co-workers
successfully performed the direct ATRP of sodium acrylate in
water 169 using an oligomeric PEO initiator and the CuBr/2,2-
bipyridine system, obtaining low-molecular-weight polymers (up
to 7400 Da) with low polydispersities (1.20−1.30). The blocking
efficiency of the systems has not been investigated. Surprisingly,
this strategy has received little attention, and its use seems to be
restricted to the functionalization of various surfaces with
poly(acrylic acid) brushes.170,171 To our knowledge, the
synthesis of amphiphilic block copolymers by direct ATRP of
sodium acrylate has not been reported yet, probably due to the
difficulties in finding a proper solvent for both the hydrophobic
and the hydrophilic partners.
The most common approach remains the synthesis of block
copolymer containing polyacrylic or polymethacrylic acid as
hydrophilic block, starting from the corresponding tert-butyl
ester, which can be readily polymerized via ATRP. The resulting
polyester can be quantitatively converted to the corresponding
polyacid, by thermolysis or by hydrolysis, by the already
mentioned procedures such as HCl in dioxane/water mixture
or TFA in CH2Cl2. Matyjaszewski’s group first reported the
successful preparation of amphiphilic block copolymers (diblock,
star, ABA, and ABC triblock) by ATRP following this approach,
utilizing either tert-butyl acrylate (tBA)81,172 or tert-butyl
methacrylate (tBMA).151 The polymerization of tBA displays a
good living character up to relatively high molecular weight (50
KDa) and good blocking efficiency when poly(tert-butyl
acrylate) (PtBA) is used as macroinitiator. Both addition of
small amounts of Cu(II) and use of polar solvents (which
enhance the solubility of the deactivator) decrease the reaction
rate and afford polymers with narrower MWD.
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In Table 1 are listed relevant systems based on acrylic and
methacrylic acid diblock amphiphilic polymers prepared by
ATRP, whose surface properties have been evaluated. Diblock,
triblock, and three-arm star 1a (with a quite extended range of
molecular weights and low polydispersities) have been prepared
via ATRP with a standard CuBr/PMDETA catalytic system in
bulk, either starting from the styrenic98 or the acrylic block.97
Several studies have been performed to find the optimal
conditions for the polymerization to occur with reasonable
rates, high molecular weights, and low dispersities. The CuBr/
PMDETA systems proved to work better for the synthesis of
PtBA macroinitiator in a polar solvent (dibenzylether) and in the
presence of small amounts of CuBr2 as deactivator.81
The importance of using a brominated initiator has been
claimed in the case of 20a,82 given the fact that chlorides are not
able to provide fast initiation for ATRP of acrylic monomers.173
However, synthesis of 20a with low polydispersity (1.1 < PDI <
1.3) up to MW = 60 000 has been achieved preparing a PMMA−
Cl macroinitiator with a RCl/CuCl/HMTETA system and
switching to CuBr/PMDETA for the tBMA polymerization.155
The bromide allows for fast initiation, but the minor liability of
the R−Cl bond over the R−Br one allows for better control over
molecular weight distribution, by minimizing secondary
reactions. CuCl proved to be superior to CuBr in CuX/
PMDETA-catalyzed ATRP of tBMA on a PS−Br macroinitiator,
again due to halogen-exchange effects.83
Double hydrophilic block copolymers based on a poly-
methacrylic acid block also can be prepared by ATRP. These
kinds of polymers show useful pH-dependent micellization
properties, due to the selective ionization of one of the two
blocks at a different solution pH. 21a block copolymers have
been prepared with low dispersities in usual ATRP conditions.
Hydrolysis of the tBMA block is achieved with HCl/dioxane,
without affecting the PDEAEMA block.77
ATRP synthesis of 3 was reported more recently.95,125,127 The
copolymers have been prepared starting from a PBA−Br
macroinitiator and growing a PtBA block, either in homogeneous
conditions95 or in emulsion.127 Hydrolysis conducted in the
presence of TFA selectively and quantitatively removes the tert-
butyl groups without affecting the ester group in the BA units,
contrarily to the HCl/dioxane system.95 Growth of PBA on
PtBA−Br macroinitiator is also possible.128Pyrene-labeled 6 and
22 were synthesized in a three-step procedure, by preparing a
HO−PCL−Br macroinitiator by means of a Sn(Oct)2-catalyzed
ROP, initiated by a difunctional brominated alcohol. Sub-
sequently, tBMA or tBA blocks were grown via ATRP and the
products were hydrolyzed. The pyrene unit was added by
esterification with a pyrene-containing carboxylic acid just before
the hydrolysis step.90 Copolymerization of BA and tBA in ATRP
conditions gives a statistical polymer. Both monomers display the
same polymerization rate.136 Narrowly dispersed tBA homo- and
block copolymer 3a has also been prepared by FeCl2·4H2O-
(PPh3)2-catalyzed ATRP in acetone.129
Anionic Polymerization. Living anionic polymerization has
been extensively used to prepare amphiphilic block copoly-
mers.23,76 Before the development of living radical methods,
which require less harsh conditions, anionic polymerization was
the most used technique to obtain well-defined polymers with
low dispersities. A broader choice of hydrophobic partners is
available, including in particular aliphatic olefins, which cannot be
polymerized with controlled radical polymerization techni-
ques.23 Relevant examples are listed in Table 1. PIB can be
conveniently synthesized by cationic living polymerization. The
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capped PIB block can therefore be converted in an anionic
macroinitiator. Thiophene has been found to be a suitable
capping agent, which is more successful compared to furan
(known to lead to unwanted secondary reactions).159 Reaction of
thiophene-terminated PIB with n-BuLi provides an efficient
macroinitiator for anionic polymerization of tBMA. The
polyisobutylene hydrophobic block is usually synthesized by a
cationic procedure using BCl3/TiCl4 catalyst. The polymer is
capped with DPOMe, and the following block of poly(tert-butyl
methacrylate) is prepared by polymerization in anionic
conditions, using Na/K alloy in dry tetrahydrofuran (THF) to
create the active species.121 The blocking efficiency is higher than
95%, and the dispersity is very low (PDI = 1.06−1.13). Double
hydrophilic 25 was synthesized by anionic polymerization of the
protected monomers (4-tert-butoxystyrene (tBOS) followed by
tBMA), and the product was completely hydrolyzed with HCl in
water/dioxane, in standard conditions.161 Capping of the first
block with DPE and the addition of LiCl are required to ensure a
well-defined character of the second tBMA block. Eisenberg’s
group studied extensively 1 copolymers of various compositions
prepared by anionic living polymerization using sec-butyllithium
as initiator.91−94,100−111,174 LiCl and α-methylstyrene were used
to prevent side reactions during polymerization of tBA.91,174 The
hydrolysis of the tBA block was performed with p-toluenesul-
fonic acid (pTSA) in refluxing toluene. Block copolymers with a
broad range of compositions and low dispersities have been
successfully prepared, allowing a systematic and extensive study
of their properties. Polymers with long PS chains (170−2300
units) and short PAA blocks (8−360 units),94,103,110 as well as
short PS (6−110 units) attached to long PAA (270−2360
units),100,102 have been synthesized. A triblock 18a has also been
prepared by an analogous procedure.108
According to one of the first reports on anionic synthesis of
19,93 the polystyrene block has to be capped with 1,1-
diphenylethylene to avoid side reactions. As initiator, sec-
butyllithium, in combination with α-methylstyrene and LiCl, is
effective in avoiding broad molecular weight distributions.154 In
the synthesis of a PMAA-based amphiphilic polymer containing a
fluorinated block (26), the tert-butyl group was removed by
thermolysis. Subsequently, the formed anhydrides were hydro-
lyzed in alkaline conditions.96 PDMAEMA block can be
efficiently prepared by anionic polymerization, provided that
(diphenylmethyl)lithium is used as initiator (n-BuLi gives side
products) and LiCl is added to maintain a narrow MWD. The
living character of the PDMAEMA block has also been
demonstrated. However, the synthesis of the diblock 21a was
performed starting from a living PtBMA block and was used
successfully as a macroinitiator in the polymerization of
DMAEMA.162 2 block copolymers, with narrow dispersities,
were synthesized by anionic polymerization through initiation
with (diphenylhexyl)lithium in the presence of LiCl, followed by
sequential addition of tert-butyl acrylate (tBA) and methyl
methacrylate (MMA).124 The polymers can also be end-
functionalized by reaction of the living anion with the
bromomethyl derivative of a chromophore.
Reversible Addition-Fragmentation Chain Transfer Radical
Polymerization. Reversible addition-fragmentation chain trans-
fer (RAFT) radical polymerization techniques for the synthesis
of water-soluble and responsive amphiphilic polymers has
recently extensively been reviewed by McCormick and co-
workers, in particular from a mechanistic point of view and for
what concerns its application for the synthesis of stimuli-
responsive systems.13,38,66RAFT synthesis of various block
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copolymers, including 3 and 29, was reported for the first time
in 1999.79 3 was prepared by direct RAFT polymerization of
acrylic acid (AA) to completion, followed by polymerization of
BA in a one-pot procedure.130,131 To achieve high conversions,
the chain transfer agent (CTA) has to be carefully selected.
Indeed, when dithiobenzoate esters are used as CTAs,
conversion rarely exceeded 30%. This behavior has been
explained by the stabilizing effects of the phenyl group on the
intermediate radical formed during the addition-fragmentation
step or, alternatively, by the formation of a terminating adduct
between the intermediate radical and a propagating radical.
Xanthates and trithiocarbonates proved to be better CTAs for
RAFT of AA in alcohol or water/alcohol mixtures.175 However,
the one-pot procedure is only possible for short PAA chains
(20−50 units), because transfer to the solvent occurs to a
significant degree at high conversions when the [AA]/[CTA]
ratio is high.130 The possibility of a RAFT synthesis of 3 in
emulsion conditions in water, with a good control over the
dispersity, has been demonstrated.132 An amphiphilic RAFT
agent and controlled feeding of the second monomer (starve-
feed) are required to avoid droplet nucleation.176 Preparation of
1 112 and 5 copolymers by RAFT/MADIX has been
reported.117,137−139 Respectively, 1b and 5a were first synthe-
sized in aqueous emulsion and then hydrolyzed in basic
conditions (NaOH at 90−95 °C). Small amounts of AA are
added for the synthesis of the second PEA block (for
polymerization stability). Nevertheless, the dispersity indices
are always greater than 2. The RAFT/MADIX can also be
performed by synthesizing a PBA macroinitiator (1K−3K Da) in
ethanol and then growing the PAA (3K−12K Da) block in the
same solvent in a one-pot synthesis. This was achieved through
the use of xanthate 2-mercaptopropionic acid methyl ester o-
ethyl dithiocarbonate (Rhodixan A1, Rhodia) as the RAFT
agent.133−135 With the same protocol, 10 was successfully
synthesized.142,143 1 was synthesized by RAFT in dioxane with 2-
[(dodecylsulfanyl)carbonothioyl]sulfanyl propanoic acid. The
conversion reached 40% for AA and 10% for styrene.116 Short
PAA10-b-PS1−10 was synthesized with the same procedure.117,118
1, 19, and 30 can be synthesized in either water or dioxane using
in all cases 4-cyano-4-thiothiopropylsulfanyl pentanoic acid
(CTPPA) as a control agent and 4,4′-azobis-4-cyanopentanoic
acid (ACPA) as the initiator.78 This is, to the best of our
knowledge, the first report of RAFT synthesis of PMAA in water.
A PAA macroinitiator was prepared with 2-dodecylsulfanylth-
iocarbonylsulfanyl-2-methyl propanoic acid as RAFT agent and
AIBN in THF (61 units). PS block (132−704 units) was grown
in MeOH in a second step, after purification of the PAA block,
with a RAFT dispersion polymerization.119
Nitroxide-Mediated Polymerization. Nitroxide-mediated
polymerization (NMP) is one of the first and conceptually
simplest controlled radical polymerization techniques. It only
involves the reversible deactivation of the propagating polymer
radical through reaction with a stable radical generated in situ by
the nitroxide.74 Even though in some aspects it has been
surpassed by the more sophisticated ATRP and RAFT, NMP still
attracts interest because of its broad range of applicability, the
limited amount of additives required (basically, only the
nitroxide) with respect of the other controlled polymerizations,
and the relatively mild conditions. Scope and limitations of NMP
have been reviewed recently.75
Charleux and co-workers have reported the first direct
nitroxide-mediated polymerization of acrylic acid in the presence
of SG1/DEPN (1-(diethoxyphosphinyl)-2,2-dimethylpropyl-
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Table 2. Amphiphilic Block Copolymers Containing an Aromatic Sulfonate Block
1,1-dimethylethyl nitroxide) and dioxane as solvent to avoid
transfer reaction.177 Moreover, a short poly(acrylic acid) with a
narrow molecular weight distribution, prepared by SG1
nitroxide-mediated controlled free-radical polymerization, was
recently used for chain extension with styrene and n-butyl
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acrylate, demonstrating the ability of the homopolymer to initiate
the polymerization of a second block.178
1 was successfully synthesized via NMP of a PS macroinitiator
and direct polymerization of AA.113 The same group reported
NMP of block 1 and 3 latexes with short AA block (14−38 units)
and long hydrophobic block, by using a nitroxide-terminated
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PAA macroinitiator in a water emulsion and surfactant-free
conditions at alkaline pH.114,115 The same procedure was used to
prepare 11.144
Also diblock, triblock, and star amphiphilic 1 copolymers has
been prepared by SG1-mediated NMP of a PS macroinitiator and
chain extension with PtBA, followed by hydrolysis.89 In this case,
a small amount of styrene is added in the second polymerization
step to decrease the propagation rate, which results in
incorporation of some styrenic units in the PtBA block. 12 has
also been prepared by NMP, through SG1/DEPN-mediated
polymerization of tBA and chain extension with isoprene,
followed by hydrogenation with sulfanyl hydrazide and
deprotection in acidic conditions.145
Group Transfer Polymerization. Group transfer polymer-
ization (GTP) has been limitedly used for the synthesis of acrylic
acid-based amphiphilic polymers. As for ATRP, protection of the
carboxylic group is required, because of catalyst deactivation by
means of the free acid. Most of the reports of amphipihlic
polymers prepared by GTP appeared in the literature in the
1990s. Nowadays ATRP and RAFT, which provide better
control over molecular weight distribution and architecture, have
almost completely replaced GTP for the preparation of acrylic
acid-containing block copolymers. Patrickios and co-workers164
synthesized random, diblock, and triblock copolymers contain-
ing DMAEMA (27) and MAA by GTP, using trimethylsilyl
(TMS)- or tetrahydropyranyl (THP)-protected acrylic acid as
precursors of the PMAA block (27b and 27c). Similarly, Armes
and co-workers prepared 31168 and 27165,166 using tBMA and
THPMA, respectively, as the starting monomer for the acid
block. 20 was also synthesized by GTP of 20a and subsequent
hydrolysis.156
3.1.2. Aromatic Sulfonate Blocks. Well-defined polymeric
surfactants containing an aromatic sulfonate block have been
prepared by controlled polymerization methods. Relevant
examples are summarized in Table 2.
Atom Transfer Radical Polymerization. Analogously to
acrylic acid-based copolymers, poly(styrene sulfonate) blocks
can be prepared by ATRP of protected styrene sulfonate (e.g.,
ethyl ester), followed by thermolysis or hydrolysis, usually in
basic conditions. 34 has been recently synthesized by ATRP of
the corresponding neopentyl ester, followed by thermolysis at
150 °C.179 A PSSNa macromonomer has been successfully
prepared by ATRP of styrene sulfonate ethyl ester, which was
subsequently hydrolyzed with NaOH in dimethylformamide
(DMF)/water or KOH in DMF.197 Ethyl and dodecyl esters of
styrene sulfonic acid brushes have also been grown by ATRP.198
However, direct ATRP of sodium styrene sulfonate has also been
reported199,200 and very recently has been successfully used to
synthesize 35 with different HLBs.180,181
The ATRP of SSNa in water is not a true living process,
because of the competitive coordination of solvent and ligand to
the copper species.200 Nevertheless, the polymerization with
CuBr/bpy catalytic system and a water-soluble initiator proceeds
very fast and, initially, with a bimodal distribution. However, the
final dispersity is not high (1.2−1.6). Addition of Cu(II) and the
use of water/methanol mixtures as solvent gives better results in
terms of dispersity indices. A halogen-exchange effect has been
proposed also for this system.199
Nitroxide-Mediated Polymerization. Sodium styrene sulfo-
nate can be directly polymerized by 2,2,6,6-tetramethylpiper-
idine-1-oxyl (TEMPO)-mediated polymerization in a water/
ethylene glycol mixture.182 High molecular weights (up to 900
KDa) and low dispersities can be obtained. The PSSNa prepared
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by this procedure can be used as a macroinitiator for the growth
of a hydrophobic block such as PS in emulsion183 to afford 36,
polyvinylnaphthalene in homogeneous conditions using dime-
thylsulfoxide (DMSO) as solvent188 (37), or other styrenic-type
blocks of various hydrophilicities184 (38−42). DEPN has been
used more recently for the synthesis of 36, starting from a PS
macroinitiator and adding the PSSNa block in three steps,
passing through the neopentyl and the trimethylsilyl derivatives
of SS.185,186
Reversible Addition-Fragmentation Chain Transfer Radical
Polymerization. Since the very first report of RAFT polymer-
ization, 201 the possibility to prepare PSSNa by this procedure has
been demonstrated. However, few examples concerning RAFT
of PSS containing amphiphilic block copolymers have been
reported. A tunable double hydrophilic copolymer 42 has been
prepared and studied by Mitsukami et al.189 The efficiency has
shown to be highly dependent on the nature of the CTA for the
polymerization of SS in aqueous media: while 4- cyanopentanoic
acid dithiobenzoate-mediated RAFT yielded a poly(sodium 4-
styrene sulfonate) homopolymer with a narrow molecular weight
distribution (Mw/Mn = 1.17) and a molecular weight close to the
theoretical value, carboxymethyl dithiobenzoate-mediated
RAFT yielded a homopolymer with a broad molecular weight
distribution and average molecular weight significantly higher
than the theoretical value. Interestingly, the conversions are
almost identical for the two polymerizations. Recently, RAFT has
been used to prepare PSS-TOA, which can be subsequently used
as a macro RAFT agent for a second block of PS of various
lengths. The controlled nature of both polymerization steps has
been emphasized.187 This system can be easily converted to the
corresponding Na salt by ion exchange. The use of the TOA salt
of styrene sulfonate is required to solubilize the monomer and
perform the polymerization in a nonpolar organic solvent.
Polystyrene Sulfonation. Sulfonated polystyrene block
copolymers have also been prepared by the postpolymerization
sulfonation of polystyrene. This represents the oldest approach
to the synthesis of PSS-containing block copolymers. However, it
is difficult to achieve 100% sulfonation of the PS block. Side
reactions can occur during the postpolymerization sulfonation,
giving rise to intramolecular sulfone linkages,202 and it is not
always possible to selectively sulfonate the PS block. For
example, polydienes are more reactive under polystyrene
sulfonation conditions and can be selectively sulfonated in the
presence of polystyrene using a sulfur trioxide/1,4 dioxane
complex.203 Nowadays, other procedures involving polymer-
ization of sulfonated styrene are preferred. Diblock 43 and
triblock 44 of various compositions can be prepared by
sequential anionic polymerization of tBS and styrene and
subsequent sulfonation.190,191 The sulfonation, usually carried
out with SO3 complexed in an opportune solvent (triethyl
phosphate in 1,2-dichloroethane), is selective toward the styrene
and gives good conversions (80−100%). With an analogous
procedure, which also involves the catalytic hydrogenation of the
polyolefinic block prior to the sulfonation step, 45 has been
prepared.192,193 If H2SO4/P2O5 is used, the degree of sulfonation
is high but side reactions are observed that lead to a broadening
of the MWD. Acetyl sulfate is less effective but more selective.
However, H2SO4/P2O5 was used more recently in the
preparation of 46, giving polymers with an average to good
degree of sulfonation (0.68−0.92) and narrow distribu-
tions.194−196
3.1.3. Polyvinylpyridines and Quaternized Arylamines
Blocks. Polyamine blocks also include polymerized vinyl-
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Table 3. P2VP- and P4VP-based Amphiphilic Block Copolymers

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pyridine or styrene derivatives that contain amino groups
attached to the phenyl ring. The amino group can also be
present as a quaternary ammonium salt. The latter class of
compounds is usually derived by postsynthetic quaternization of
the corresponding polyamine precursor (Table 3). Direct
measurements of surface activity of such systems are very rare,
but there are several studies concerning formation of micelles
and stabilization of particles in water solution. The most studied
systems of this kind are 47 and 49 and their derivatives. There are
also reports of polyvinylpyrrolidone (PVP)-based block
copolymer with different hydrophobic blocks (Table 3). The
aggregation behavior of these polymers is obviously pH-
dependent. The PVP ring is often quaternized after synthesis
to get a permanently charged quaternary ammonium block.
TEMPO-mediated NMP of 4VP has been found to proceed in
a controlled manner,208,221 and the resulting polymer has been
used successfully as a macroinitiator for hydrophobic blocks such
as styrene208 and dimethylacrylamide (DMA).218 The use of
DEPN instead of TEMPO allowed the synthesis of 53 with
longer DMA blocks.219 The polymerization of 4VP requires high
temperatures (>125 °C) and gives slightly broader MWD
compared to those obtained with styrenic monomers208 or
anionic methods.221 Also in these cases, subsequent quaterniza-
tion of the 4VP ring with various groups has been achieved by
reacting the polymer with alkyl bromides in boiling EtOH.218
Direct polymerization of quaternized 4VP cannot be carried out
because of the instability of the ammonium salt in the
polymerization conditions. 218
Once the possibility to polymerize 4VP via ATRP was
disclosed,217 block copolymers have been prepared in this way,
such as 53217 and 49.206 However, because of the competitive
complexation of copper with the pyridine ring, which deactivates
the catalyst, a ligand with a very high binding constant for copper,
such as Me6TREN, is required.206,217 Also RAFT has been used
with good results to make di- and triblock copolymer based on
P4VP and styrene.207Vinylbenzyl chloride can be block
copolymerized by controlled radical polymerization mediated
by TEMPO, giving reactive polymers with narrow MWDs.220
This approach has been used to prepare diblock PS-b-PVBC 54,
which has been further modified by reaction with a secondary
amine to give permanently positively charged blocks.220,222,223
The resulting MWDs are higher than those usually obtained for
styrene. This behavior has been explained in terms of side
transfer reactions between the capping agent and the
chloromethyl group.222
To avoid broadening of the MWD by side reactions, other
authors prepared similar systems via RAFT polymerization of
styrene, followed by VBC and subsequent reaction with tertiary
amines.224 In this case, better results in terms of MWD have been
obtained. It is important to remark that, for polymerization of
VBC, other controlled methods such as cationic, anionic, or
ATRP are precluded because of interactions with the
chloromethylenic group.224 For these reasons, Patra et al.225
proposed the synthesis of VBC-containing diblock copolymers
via reversible iodine transfer polymerization (RITP, Figure 4).
N,N-dimethylvinylbenzylamine and the corresponding quater-
nary ammonium salt can be directly polymerized and block
copolymerized by RAFT, as demonstrated by Mitsukami et
al.189,226
3.1.4. Poly(ethylene glycol)/Poly(ethylene oxide)
Blocks. Amphiphilic copolymers based on poly(ethylene
oxide) (PEO) moieties represent by far the first and most
studied class of polymeric surfactants. Many di- and triblock
8518
Review
Figure 4. Representation of RITP mechanism. Reproduced with
permission from ref 225. Copyright 2010 Elsevier.
copolymers of PEO and PPO with a variety of compositions and
molecular weights have been present in the market as industrial
surfactants for a long time (e.g., Pluronic by BASF). Several
reviews concerning their properties have appeared in the last two
decades.5,6,8,9,21−23,122 PEG/PEO polymers are synthetized
mainly by two methods: condensation of ethylene glycol (EG)
or ring-opening anionic polymerization of ethylene oxide.
Indeed, it is common to refer to PEG when the polymer is
synthesized by the former way and to PEO if the polymer derives
from the latter. The synthesis of PEG (or PEO) is very well
established, and today, systems characterized by a broad range of
molecular weight and different terminal groups, as well as some
of their corresponding block copolymers (e.g., Pluronic series),
are commercially available. For this reason, the preparation of
new PEG-based amphiphilic copolymers is normally accom-
plished by addition of the hydrophobic block on a preformed,
commercially available PEG macroinitiator. Some examples of
amphiphilic copolymers synthesized starting from a PEG
macroinitiator are listed in Table 4.
Depending on the polymerization method, modification of the
terminal group of the PEG moiety might be necessary prior to
starting the synthesis of the second block. Hydroxy-terminated
PEG has been used directly as a macroinitiator of anionic
polymerization (for example, of acrylic monomers227) or ring-
opening polymerization for the synthesis of PEG-b-PLA228). The
terminal hydroxyl group can be easily modified to obtain the
proper initiator for a selected kind of polymerization
(dithiocarboxylate for RAFT or halogen for ATRP). 4-
Cyanopentanoic acid dithiobenzoate-terminated PEG has been
prepared and used as a macroinitiator for RAFT polymerization
of N-acryloyl-2,2-dimethyl-1,3-oxazolidine;229 halogen-termi-
nated PEG has been used as an ATRP macroinitiator for
amphiphilic block copolymers such as 56,230 57,231 58, 59 and
60,232 61,233 and a series of amphiphilic or double hydrophilic
block copolymers 65−71.234 PEG has also been used as
precursor of a thiolate for subsequent anionic polymerization
of propylene sulfide.235,236 However, especially in the case of
nonlinear or multiblock structures, sequential anionic polymer-
ization is often used. 237 PEO-b-PS (58),237,238 72, 73,235,236
74,239 and 75240 have been prepared in this way.
HEUR. Hydrophobically modified polyurethanes (HEUR)
have been extensively studied in fundamental research aimed at
understanding the aggregation behavior of associating polymers.
Here again we focused on the systems of which either the CMC
or the CAC have been measured.
The polymers (see Table 5) can be prepared by a two-step or
single-step reaction.241 In the two-step method, an excess (a large
excess is used to suppress the dispersity index (PDI) of the
product) of the diisocyanate is reacted with poly(ethylene oxide)
(PEO) to produce an isocyanate-functionalized polymer. This
polymer is subsequently functionalized with hydrophobes by the
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Table 4. PEG-Containing Macrosurfactants

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Table 5. Ethoxylated Polyurethanes: Structures of the Studied Systems

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Table 6. Amphiphilic Block Copolymers Derived from Alkylaminoacrylates

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Table 6. continued

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Table 6. continued
reaction with aliphatic alcohols. The single-step method involves
the reaction of PEO with a monoisocyanate containing a
hydrophobic group. The PDIs of the synthesized polymers are
close to the PDIs of the parent PEO polymer.
3.1.5. Alkylaminoacrylate Blocks. Several amino deriva-
tives of acrylic acid have been employed for the synthesis of
amphiphilic block copolymers. The most studied systems are
shown in Table 6. These kinds of block copolymers have
attracted much interest because of their pH-dependent hydro-
philicity and for the possibility to easily change the characteristics
of the pendant amino group by subsequent postsynthetic
functionalizations. For example, they can be straightforwardly
quaternized to give permanently positively charged or
zwitterionic blocks (see Table 6).
The most employed alkylaminoacrylates for the preparation of
amphiphilic polymers are DMAEMA and DEAEMA. Armes’
group, who pioneered the investigations of this kind of system,
8523
Review
prepared several amphiphilic block copolymers containing a
PDMAEMA moiety by GTP and ATRP polymeriza-
tion.39,67−69,254−258,266,270,276,278,279 ATRP proved to be more
versatile than GTP, allowing the synthesis of block polymers with
comonomers other than acrylates.280 In addition, in GTP-based
synthesis, significant amounts of homopolymer can be found,
which makes the purification steps problematic.254 Homopol-
ymer of DMAEMA can be prepared by ATRP either in organic
solvent280 or in water.281 The kinetic plots show fast initiation
and negligible terminations. It has been reported that DMAEMA
and other alkylaminoacrylates can undergo unwanted trans-
esterification with methanol at room temperature if it is used as
solvent.282 The problem can be easily circumvented by using the
more sterically hindered isopropanol, by increasing the reaction
temperature, or by using water as cosolvent, which sensibly
increases the polymerization rate.262,282
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Table 7. Amphiphilic Block Copolymers Based on Miscellaneous Acrylates

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Table 7. continued

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Table 7. continued
In the synthesis of amphiphilic block copolymers, the situation
is more complicated. The PMMA−Br macroinitiator shows poor
blocking efficiency, due to elimination of HBr from the tertiary
terminal carbon, so the more stable PMMA−Cl has to be used
instead.263 On the other hand, initiation from PMA is relatively
slow compared to the propagation of PDMAEMA (halogen is on
a secondary carbon), so in this case the brominated macro-
initiator is used. The system works quite well, provided that CuCl
is used as catalyst, taking advantage of the halogen exchange. A
PS macroinitiator gives the broadest MWD.263
8526
Review
Well-controlled ATRP of PDEAEMA initiator and 100 has
also been carried out successfully with p-TsCl/CuCl/HMTETA
in water/methanolic solutions.274,283 Similarly, an aldehyde-
terminated 100 was synthesized by ATRP.275
Problems of slow initiation have been found also in the ATRP
of 99.273 Also in this case, halogen exchange provides better
results. PDMAEMA-containing block copolymers can also be
made by living anionic polymerization157,261 and TEMPO-
mediated free-radical polymerization.267 The latter method has
been used for the synthesis of 94, but the polymers obtained have
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broad MWDs and the reaction failed in the attempt to prepare
the homopolymer of DMAEMA.267
Homopolymerization and block copolymerization of DMAE-
MA by RAFT has been investigated,284 but to the best of our
knowledge no synthesis of block copolymers with a permanently
hydrophobic block has been reported yet, although several
examples of block copolymers responsive to pH and/or
temperature can be found.38,71,285,286
Quaternization. PDMAEMA blocks can be quite easily
quaternized in several ways. Betainization with propane-1,3-
sultone, in order to obtain zwitterionic derivatives, has been
performed.255,260,276 The reaction is selective for DMAEMA in
presence of DEAEMA and DPAEMA blocks when performed in
mild conditions.276 Quaternary alkyl amines can be obtained by
coupling with alkyl halogenides, such as MeI,266 ethyl, pentyl,
heptyl, n-propyl, n-butyl and tert-butyl bromides,261 and octyl
bromide,273 with nearly quantitative yields.
3.1.6. Other Water-Soluble Acrylate Blocks. Several
other acrylic monomers have been successfully used as
hydrophilic partners in amphiphilic block copolymers for various
purposes, usually by means of living controlled radical or anionic
methods (see Table 7). In some cases, surface/interface activities
of the resulting polymers have been evaluated (a list of recent
examples is provided in Table 7).
From a synthesis point of view, each system represents a
particular case. Nevertheless, especially in the last few years,
ATRP seems to be the preferred way to prepare well-defined
amphiphilic block copolymers based on acrylates. Regardless of
the polymerization method, the critical factor is usually the
choice of the solvent. Common solvents for hydrophilic and
hydrophobic monomers can be found in some cases,303,304 such
as THF,301 dioxane,303 DMF,309 DMA,303 NMP,303 methanol,
and isopropanol,294 either alone or in combination with water.
In most cases, mixtures of water and alcohols are able to
dissolve both the hydrophilic and the hydrophobic monomers
(or macroinitiators). In a quite general way (and in particular in
all the cases examined here), ATRP is faster in water than in
alcoholic media, but the process seems to be not truly controlled,
leading to broad MWDs. Alcohols slow down the polymerization
and provide a better living character, which results in better
blocking efficiency and narrower distributions.293,295,311 Gen-
erally speaking, for ATRP in water/alcohol mixtures, the rate
increases with the polarity of the solvent, which can be tuned by
varying the water/alcohol ratio or using alcohols of different
polarities (commonly, isopropanol and methanol).294 Because of
the better control, even if the polymerizations in some cases can
be conducted in pure water, a mixture is often preferred.311 For
example, in the preparation of 2-methacryloyloxyethyl phos-
phorylcholine (MPC) homopolymers by ATRP, it has been
observed that the monomers polymerize even in the absence of
any ATRP initiator in aqueous solution at 20 °C, due to
impurities in the water phase that are able to start free radical
polymerization.295 In methanol the rate of ATRP is much slower,
but fortunately autopolymerization of MPC does not occur in
this solvent.294,295 Homo-, di-, and triblock (co)polymers based
on the hydrophilic MPC have been prepared in methanol and
water−methanol mixtures.296−300
Garnier and Laschewsky performed the synthesis of various
acrylic neutral, cationic, and anionic amphiphilic block
copolymers, characterized by increasing polarity of the hydro-
philic group, by the RAFT/MADIX procedure.303,304 Benzyldi-
thiophenyl acetate was employed as the RAFT agent, as it is
known that dithioesters and trithioesters are good RAFT agents
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for acrylic monomers.303 In addition, the dithiophenyl acetate
residue should minimize retardation effects in the polymer-
ization.316 The synthesis of poly(butyl acrylate) exhibited a much
shorter induction period than reported for the classical
dithiobenzoates as chain transfer agents.303,304
Several examples of PEGMA-based amphiphilic copolymers
have also appeared in recent literature.307−313,317 These kinds of
polymers have received great interest in the past few years.318
They can be considered analogous to PEG-based copolymers,
resembling them from a chemical point of view, but with the
advantage of being polymerizable via mild controlled radical
methods. Also, they give access to more complex graft/comb/
brush structures, with the possibility to tune their characteristics
by changing the length of the pendant oxyethylene group. In
most cases, the polymers are prepared by ATRP (see Table 7).
Concerning copper(I)-mediated ATRP in the presence of
oxyethylene groups, it has been shown that polymerization of
poly(ethylene glycol)methyl methacrylate monomer (MeO-
PEGMA, molecular weight = 480 g mol−1) can be conducted in
toluene. The polymerization is mediated by copper(I) bromide/
N-(n-propyl)-2-pyridylmethanimine as the catalyst and is fast
relative to benzyl methacrylate (BzMA) under similar conditions.
This high rate of polymerization is ascribed to complexation of
the oxyethylene groups with copper in a dynamic equilibrium
with the pyridyl methanimine ligand complexation, resulting in a
more active catalyst.312,319
When the difference in hydrophilicity of the two partners is too
different (like in the case of strong electrolytes), the polymer-
ization of a neutral precursor of the hydrophilic monomer and
subsequent modification is the usual approach. For example, in
the synthesis of a block copolymer of poly-
(diethyldisilacyclobutane) (PDESB) and poly-
(sulfopropylmethacrylate) 106, a nonionic diblock copolymer
PDESB-PtBMA was synthesized first; this was converted to a
weak polyelectrolyte block copolymer PDESB-PMAA, and then
the weak acid groups were changed to a strong acid group by
reaction of propanesultone.292 An analogous method had been
utilized before for the synthesis of 107.289,290
A slightly different procedure was used for the postsynthetic
esterification of the hydroxyl group of HEMA with a sulfonated
benzoic acid, to obtain 135.306 Reports of controlled block
copolymerization of acrylamide and N-isopropylacrylamide were
absent in the literature until very recently.314,315
3.2. Synthesis of Polysoaps
The general strategy for the synthesis of polysoaps is exhaustively
covered in the seminal review of Laschewsky, to which the reader
is referred.4 Although this work was published in 1995, there are
no significant new developments in the approach used: the
synthesis of polysoaps is normally not very challenging, being
performed mostly via very well established free radical
polymerization or polycondensation methods.4 In most cases,
no particular attention is paid to the precise control of the
macromolecular structure, but in the recent literature there are
few exceptions in which the copolymers are prepared via
controlled radical processes such as NMP320,321 or RAFT.322,323
The most common kinds of polysoaps for which surface
properties have been investigated are based on amphiphilic
derivates of acrylamide or acrylic acid and on hydrophibically
modified polysaccharides. Other systems include homopolymers
of polymerizable surfactants320,324 or random copolymers of
hydrophobic and hydrophilic monomers.325 The hydrophobic
monomer can also be pH-responsive. 326
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Table 8. Acrylamide-based Polymeric Surfactants: Structures of Studied Systems

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Table 8. continued
3.2.1. Polyacrylamides and Related. Almost all of the
literature references on hydrophobically modified polyacryla-
mides (HMPAMs) included in the review by Wever et al.327
consider the thickening capability of the polymers in aqueous
solution. However, here we focus on the interfacial properties of
these polymeric materials. Although most of the publications do
not discuss the interfacial properties of the materials, their critical
association concentration (CAC) and/or critical micelle
concentration (CMC) do give information on their ability to
perform as interfacial agents.
Most of the acrylamide-based polymeric surfactants (Table 8)
are synthesized via free radical polymerization. The differences
lie in the conditions employed during the synthesis. For example,
polymers 142 and 143 (random copolymers) are both prepared
in dimethylformamide (DMF) through free radical polymer-
ization,328,329 while polymer 144 (random copolymer) is
prepared in water.43
Another method widely used is the micellar copolymerization
technique.330,331 Here the reaction medium is water and the
hydrophobic monomer is dissolved using surfactants (the most
commonly used surfactants are sodium dodecyl sulfate (SDS)
and cationic hexadecyltrimethylammonium bromide (CTAB)).
The drawback of the micellar copolymerization method is the
purification step that is necessary to remove the surfactants. This
can be avoided by employing a method, closely related to the
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micellar technique, involving micelle-forming polymerizable
surfactant monomers.59−61,332 However, to identify suitable
surfactant monomers for the desired structure remains a
challenge. A relatively new method is the template polymer-
ization. This method involves the use of a template onto which
the comonomer is polymerized. The structure of the polymer is
determined by the template. The advantage of this method over
the micellar copolymerization is the ability to introduce longer
hydrophobic blocks.42,333
3.2.2. Hydrophobically Modified Polysaccharides.
Polysaccharides are suitable starting materials for the preparation
of polysoaps, due to their broad availability and the presence of
easily functionalizable hydroxyl groups that can be used to
introduce hydrophobic moieties in the hydrophilic backbone.
As for polyacrylamide, these systems are often used as
thickeners for water solutions,327 but also their surface/interface
properties have been the subject of many studies for applications
in emulsion stabilization and similar. The backbone is usually
constituted by hydroxyethyl-357−360 or carboxymethyl 361
cellulose, dextran,362−365 carboxymethylpullulan,366,367 inu-
lin,368,369 pectin,370 and chitosan.371 The hydrophobic groups
can be introduced via reaction of the hydroxyl groups with
organic halogenide (substitution), epoxides (addition), or esters
(transesterification). Other more sophisticated methods are
seldom used and only for particular systems such as PLA-grafted
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Figure 5. Structures of polysaccharide-derived polysoaps
dextran. 372 The products have a random distribution of the
hydrophobic groups. In most cases the reaction is performed in
water or water/isopropanol mixtures and in the presence of
NaOH as the base.357,359,364
Hydroxyethyl cellulose (167) has been variously function-
alized with hydrophobic groups via reaction of the hydroxyl
group with an organic halogenide357 or an epoxide360 in basic
conditions, using water or mixtures of water and isopropanol as
solvent. The degree of substitution can reach values as high as 25
weight %, but above 10 weight % of substitution the polymer is
no longer water-soluble.357
Carboxymethyl cellulose (168) has been hydrophobically
modified by microwave-assisted reaction of its sodium salt with
fatty esters from rapeseed oil in DMF/water or DMF/TSA
mixtures. Slightly higher degrees of substitution were obtained
when Na2CO3 was used as catalyst.361
Pullulan (169) has been converted to carboxymethylpullulan
by reaction with sodium chloroacetate in water/IPA mixture and
in the presence of NaOH. The counterion was then exchanged
with tetrabutylammonium by neutralization and reaction with
TBAOH, and the following step of functionalization was
performed by reaction with an alkyl bromide in DMSO.366 A
similar approach (substitution with TBAOH and reaction with
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the electrophile in DMSO) was also used for the functionaliza-
tion of dextran (170) with hydrophobic epoxides362,363 and for
pectin (171) with alkyl bromides.370 In the case of dextran, in this
way it is possible to obtain higher degrees of substitution
compared to the NaOH/water system.362 Structures are
depicted in Figure 5.
3.3. Synthesis of Complex Polymeric Surfactants
Despite the large number of prepared polymeric surfactants with
complex architectures, not many of these systems have been
characterized in terms of surface activity. The general synthetic
strategies for the synthesis of copolymer with complex
architectures have been reviewed several times in recent
years.16,21−23,48,76,373−375 Here we will focus on the synthesis
of those polymeric surfactants whose surface activity in water has
been actually evaluated and related systems. Most of the complex
polymeric surfactants studied for their surface properties are
represented by comb-like, hyperbranched, and dendrimeric
copolymers, but there are also some examples of gemini,
miktoarm, and star copolymers (Table 9).
In one of the early studies of surface properties of gemini
polymeric surfactants, 376 a miktoarm PS(PEO)2 copolymer 172
was prepared via two rather complicated alternative procedures
involving several protection−deprotection steps, anionic poly-
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Table 9. Structure and Composition of Typical Polymeric
Surfactants with Complex Molecular Architecture
merization of styrene and ring-opening polymerization of
ethylene oxide.
8531
Today, especially thanks to the availability of controlled radical
polymerization methods and “click” chemistry, the preparation
of geminior more in general miktoarmamphiphilic
copolymers can be achieved with simpler methodologies.23,374
For example, various PSn(PEO)m heteroarm copolymers have
been made by combinations of ring-opening polymerization of
EO and ATRP of styrene using opportune multifunctional cross-
linkers.377,378
Another strategy based on ATRP has been used by the same
group to synthesize block 3- and 4-arm star of PS-b-PEO 176 and
177 (Figure 6). The PEO blocks were made by anionic ring-
opening polymerization after modification of the terminal
bromides with ethanolamine. 379
An interesting example of the synthesis of a PMMA-PEO-PS
μ-star miktoarm polymer 178 based exclusively on ATRP was
recently reported.380 Because of the high deactivation constant
and the low propagation rate of styrene with the CuBr/
PMDETA catalyst at room temperature, the authors were able to
incorporate only one styrene-terminated PEO unit on the
macroinitiator (Figure 7).
Star block copolymers constituted by vinylic monomers both
as hydrophilic and hydrophobic partner are generally prepared
by anionic polymerization or ATRP. ATRP has been used to
prepare gemini381 and star block PS-b-PAA.99 98 The latter can
also be made by NMP.89 A 3-arm block star PBMA-
PDMAEMA268 and a star PMMA-b-PDMAEMA261 (also
quaternized on the nitrogen) were made via ATRP.
The synthesis and study of a complex PS-PAA made by ATRP,
which can be considered as a joining link between block star and
dendrimeric polymer, has been recently reported.385,386 A
schematic representation of the structures prepared is reported
in Figure 8.
The synthesis is based on the use of multihalogenated
calixarenes (Figure 9a) for the preparation of the PS core with 2−
8 arms followed by a two-step chemical modification of the
terminal bromide into a difunctional ATRP initiator for the
growth of tBMA chains (Figure 9b).
A dendrimeric PS-PAA has been also synthesized again via
ATRP, starting from a poly(propylene imine) dendrimer with 64
NH2 functionalities. The polymerization involved, as usual (see
section 3.1.1), ATRP of styrene followed by ATRP of tBMA and
hydrolysis.387 However, from their studies on the behavior of the
prepared polymers, the authors concluded that only a minor
fraction of the 64 active sites was actually initiated, leading to
polymers with a low (not specified) number of branches. On the
other hand, an initiator with 8 sites provided an 8-arm star
copolymer. Dendritic PPO-PEO polymers 184 with different
arm lengths have been prepared starting from a third-generation
poly(amido amine) (PAMAM) core by base-catalyzed ring-
opening polymerization of PO followed by EO.383 An analogous
system, but with diblock PPO-PEO (182) or triblock PPO-PEO-
PPO (181) arms, was prepared by the same approach starting
from tetraethylenepentamine (TEPA). 382 This copolymer is
constituted by a low number of arms (7), so it can be considered
more like a star rather than a dendrimer. Star amphiphilic
polymers with a higher number of arms can be conveniently
prepared by an “arm first” methodology. A series of block,
heteroarm, and random star amphiphilic copolymers with 20−80
arms based on HEGMA (methoxy hexaethylene glycol
methacrylate) and BzMA were prepared with a GTP procedure,
using a diacrylate (ethylene glycol dimethacrylate, EGDMA) for
the formation of the core, as schematized in Figure 10.388
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Figure 6. Synthesis of 3- and 4-arm star PS-b-PEO polymeric surfactants. Redrawn with permission from ref 379. Copyright 2003 Americal Chemical
Society.

PMMA-PAA copolymer 198 (Figure 11).389 First, methyl

Figure 7. Schematic synthesis of a PMMA-PEO-PS μ-star miktoarm
polymer via ATRP. Redrawn with permission from ref 380. Copyright
2009 Elsevier.
More complex architectures are also possible. An approach
completely based on ATRP has been used to synthesize a graft
methoxyacrylate (MOMA) was polymerized using CuBr/
PMDETA as the catalytic system. The resulting polymer was
subsequently acylated with α-bromoisobutyryl bromide to give a
multifunctional initiator for the growth of PMMA-grafted chains
and hydrolyzed to convert the MOMA units into AA units
(Figure 11). Starting from a tetrafunctional initiator, a star-
grafted copolymer has been made by the same procedure.390
The synthetic approach to complex structures is very
dependent on the nature of the monomeric groups that one
wants to incorporate. For example, an hyperbranched ionene (a
polymer containing quaternary nitrogen atoms in the back-

Figure 8. Schematic representation of dendrimeric PS-PAA copolymers. Adapted with permission from ref 385. Copyright 2005 American Chemical
Society.

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Figure 9. Synthesis of dendrimeric PS-PAA copolymers: (a) structure of PS core and (b) modification of end groups of PS macroinitiator for the growth
of PtBMA arms.
Figure 10. Schematic synthesis of HEGMA, BzMA, and EGDMA star
copolymers. Adapted with permission from ref 388. Copyright 2005
Elsevier.
391
bone ) has been prepared by condensation of AB2 type
monomers represented in Figure 12.392 The exact structure and
molecular weight of these polymers are not very well defined.
“Click” chemistry can represent a very versatile way to comb-
like copolymers. For example, a block-graft copolymer of
NIPAM and PCL 199 with various pendant groups has been
synthesized by ring-opening polymerization of α-Cl-CL on a
PNIPAM macroninitiator. The chlorine was then converted into
azide, and various alkynes have been attached to it via a click
reaction (Figure 13).393
Click chemistry offers a very versatile tool for the synthesis of
libraries of polymeric surfactants with various complex
architectures, as exemplified in a recent work of Ren et al.394
Other copolymers based on PCL have been prepared by previous
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Review
modification of CL with a PEO chain followed by ring-opening
copolymerization (Figure 14).395
A highly branched PNIPAM with terminal peptidic groups has
been made with a variant of the Frechet’s self-condensing vinyl
polymerization396 involving a combination of free radical
polymerization (for the backbone) and RAFT (for the
branches).397 The highly branched polymer was made in one
step by copolymerizing NIPAM and a vinyl-functionalized RAFT
initiator (see Figure 15).
The same approach has been used for amphiphilic highly
branched acrylates, but with ATRP as the polymerization
method (Figure 16).398
A combination of ATRP and oxyanionic polymerization has
been used for the synthesis of comb-like amphiphilic copolymers
based on MMA, HEMA, and DMAEMA (Figure 17).399 For the
first step of this synthesis, the authors preferred to use a silyl
derivative of HEMA, in order to decrease the difference in
polarity with MMA and achieve better control over the
polymerization. 400
An amphiphilic block-comb terpolymer containing an hydro-
phobic block of tBMA and an hydrophilic block containing
DMAEMA and a PEG-grafted acrylate was entirely made by
RAFT polymerization (Figure 18).401 The obtained polymer
204 has been further shell cross-linked via the nitrogen atoms
using 1,2-bis(2-iodoethoxy)ethane as cross-linking agent.
4. PROPERTIES OF POLYMERIC SURFACTANTS
4.1. Surface Properties
Polymeric surfactants, because of the presence of hydrophilic and
hydrophobic moieties, have been widely studied for their self-
assembling properties,373 yielding in general a huge variety of
possible micelles and similar struc-
tures.113,115,118,224,255,301,387,402−405 Aggregation of polymeric
structures into micelles or vesicles represents a crucial topic
when considering applications of these materials in the
biological/biomedical world.406−408 The general idea in this
case is to use such aggregates as loci for the dispersion/
solubilization of different chemicals and drugs.8,36,304 The subject
of micellization behavior for polymeric materials has been
extensively studied in the past 20 years and has already been
reviewed.21,58,409,410 As a consequence, in the present work, the
focus will mainly lay in the underlying factors for this behavior
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Figure 11. Schematic synthesis of copolymer 198.

Figure 12. AB2 type monomer for condensation synthesis of
multibranched polymeric surfactants.
and, mostly, on the relationship between the latter and the end-
use properties of polymeric surfactants. We start by noticing how
the aggregation provides a variety of structures and morpholo-
gies,119,411 including superaggregates and Janus particles.412 The
latter seems to indicate that the driving force for micellization is
in the case of polymeric surfactant remarkably strong and able to
overcome other counteracting forces, e.g., steric hindrance.
Indeed, this is shown by the tendency to aggregation also for
hyperbranched macromolecular architectures, as in the case of
201 P(NIPAM),397 for which steric hindrance constitutes indeed
the main factor preventing micellization. The relatively high
molecular weight of polymeric surfactants, as opposed to low
molecular weight ones, allows a fine-tuning of the micelle’s
properties. In this respect the dependence of the aggregate
structures on temperature,413 pH,77,90,95,254,414−419 external

Figure 13. Schematic synthesis of polymers 199. Redrawn with permission from ref 393. Copyright 2011 Wiley.

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Figure 14. Schematic synthesis of polymers 200. Redrawn with pernmission from ref 395. Copyright 2006 American Chemical Society.
Figure 15. Schematic synthesis of polymers 201.
Figure 16. Schematic synthesis of polymers 202. Adapted with
permission from ref 398. Copyright 2002 American Chemical Society.
shear field,420 and salt concentration70,390,421 have been reported
already and extensively studied. The kind of aggregate can be
molecularly controlled, in the case of block copolymers, by a
correct design of the blocks’ chemical structure,102,236,390,422
length,91,92,229,423 and topology.88,424 In this respect an absolute
ranking of these two factors, and even less a general
quantification of both, is still lacking in the open literature.
Figure 17. Schematic synthesis of polymers 203.
8535
Review
Indeed, Garnier et al.,303 when working on several different
copolymers of butyl acrylate 129−134 (PBA, hydrophilic block
of constant length), clearly observed how the block length and
not its chemical structure mainly determine the kind of aggregate
and mostly its size. In this case the studied hydrophilic blocks
comprised hydrophilic acrylic derivatives, including one
(positively) charged one.
On the other hand, Zhang et al.,306 when working on
copolymers with the same hydrophobic block (PBA) but a
significantly different hydrophilic one 135, were able to suggest
exactly the opposite. Indeed, they observed that the aggregation
behavior, as shown by the CMC values, as well as the surface
activity of these copolymers are predominantly determined by
the chemical structure of the hydrophilic block rather than by its
length. The CMC value is often taken as representative for the
aggregation as well as the surface activity behavior of a given
polymeric surfactant. The CMC is in most cases clearly
dependent on block length and structure. Indeed the change in
Gibbs energy for micellization (ΔGmic) is usually expressed as100
ΔGmic = −RT ln(CMC)
with R being the ideal gas constant and T being the absolute
temperature. ΔGmic is in turn a function of the chemical structure
as well as block length, with the dependence becoming explicit
when making allowance for group contribution theories, often
used for the calculation of ΔGmic values.
4.1.1. Macrosurfactants. CMC of Diblocks. Theoretical
treatments of CMC for both small molecules and macro-
surfactants predict that the CMC decreases exponentially with
the length of the hydrophobic group (or block), while the
dependence from the hydrophilic block length is much less
pronounced.425 Experimentally, it has been shown that CMC ≈
exp(−cN)where c is a parameter dependent on the Flory−
Huggins interaction parameter and N is the length of
hydrophobic group (or block)only for low N. For higher N
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Figure 18. Schematic synthesis of polymers 204.

Figure 19. Dependence of CMC from hydrophobic block length. Adapted with permission from ref 425. Copyright 2012 American Chemical Society.

Figure 20. Relationship between partition coefficient of pyrene and number of propylene units (left) and CMC (right) for Pluronic systems. Adapted
with permission from ref 427. Copyright 2000 American Chemical Society.

the dependence becomes weaker and CMC scales with
exp(−cN1/3). This behavior seems to be universal, as shown by
the data collected for several systems425 (Figure 19). A
theoretical model has been proposed to explain this dependence,
but it is based on an unusual aggregation mechanism.426 On the
basis of simple interfacial arguments, other authors found that
the CMC should scale with exp(−cN2/3).425
A good correlation between partition coefficient of pyrene in
Pluronic polymers and the number of PO units has been found
for a large number of systems (Figure 20a). Also, a linear
8536
relationship between logP and logCMC has been observed
(Figure 20b), suggesting that micellization and solubilization of
hydrophobes in Pluronic systems are favored in a similar fashion
by common factors, particularly, the size of the hydrophobic
block.427
The general principle that CMC decreases with the hydro-
phobicity of the insoluble block has been established on the basis
of several different systems. Lee and Wu393 prepared different
copolymers of NIPAM 197 (considered here the hydrophilic
monomer) with a series of caprolactone derivatives. The
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corresponding CMC values (Table 10) display a wide range of Table 11. CMC Values for Star-(block)-Copolymers of
variability depending not only on the length of hydrophobic Ethylene (EO) and Propylene (PO) Oxides 182 and 183;
block but also on its nature. Adapted with Permission from Ref 382; Copyright 2009
Elsevier)
Table 10. CMC Values for Copolymers of NIPAM and CL copolymer CMC (mg/L)
Derivatives 199 (Adapted with Permission from Ref 393;
182 [(PO)36(EO)100]7 306
Copyright 2011 Wiley)
183 [(PO)36(EO)100(PO)36]7 202
copolymer NIPAM CL CL substituted units CMC (mg/L) 183 [(PO)56(EO)100(PO)56]7 118
199a 10 13 10 5.01
10 26 16 3.31 polyelectrolytes130 and also for hyperbranched systems, like
10 33 26 2.04 184.383 The authors attribute the observed effect to hydrophobic
36 21 21 9.77 interactions present in solution. By increasing the hydrophobic
36 26 25 3.98 character of the copolymer (either by changing the chemical
199b 10 8 8 3.63 structure of the block or its length), the chains display a more
10 26 25 2.16 favorable tendency to aggregate at the CMC, thus resulting in
36 21 19 5.86 relatively lower values. It is worthwhile remarking how such
36 28 27 4.07 hydrophobic interactions might dominate over electrostatic
199c 10 31 22 7.15 repulsion as well as steric hindrance in determining the
aggregation behavior.
In this case the more hydrophobic the PCL derivative (i.e., Despite this general principle, exceptions are often reported,
benzoate vs acetate vs tetra-o-acetyl-β-D-glucopyranoside), the when complex architectures are involved. Peng et al.389 studied
lower is the CMC. This observation broadens the generality of graft copolymers of methyl methacrylate and acrylic acid (MMA/
the previous concept. As already mentioned, the dependence of AA) 198 at different molar ratios from 1.5 to 11.0 mol % AA.
CMC on the hydrophilic block length is predicted to be less They did not observe relevant changes (i.e., the observed
pronounced. This aspect is usually not extensively investigated, differences are within the experimental error for the measure-
but a systematic study of PS-b-PAA block copolymers 1102 ment) in the CMC values, which varied from 3.39 × 10−7 to 5.62
showed that the principle holds at least for this system (Figure × 10−7 g/mL in the above-mentioned interval.
21). On the other hand, polymers having roughly the same
monomer composition and molar mass, and thus the same HLB,
but different architecture can show different CMCs and surface
tension values. Gibanel et al.376 studied copolymers of PS with
PEO, namely, a linear diblock and a gemini-like one (172). CMC
and surface activity in water solution are completely different
(Figure 22). In this case the higher CMC for the gemini

Figure 21. Dependence of CMC on length of hydrophilic block for PS-

b-PAA copolymers 1 with PS block length of 11 (▲) and 23 (●) units.
Reproduced with permission from ref 102. Copyright 1995 American
Chemical Society.
CMC of Complex Architectures. The same trend in the
dependence of CMC on hydrophobic block length also has been
observed for nonlinear systems by Gong et al.382 When studying
star-(block)-copolymers of ethylene and propylene oxides 182
and 183, they observed a clear dependence of the CMC on the
relative block length (Table 11), with the CMC decreasing with
the relative length of the hydrophobic block.
In this case it is also worth noticing the change in CMC as a
function of the kind of block copolymer used, with the triblock
displaying in general lower values than the diblock one. The same
trend, i.e., decrease of CMC with more prominent hydrophobic
character, has been detected for hydrophobically modified
8537
Figure 22. Surface tension vs log(concentration) variation for the (●)
PS-b-PEO2 gemini-type 170 and (▲) PS-b-PEO linear macromonomer
surfactants. Reproduced with permission from ref 376. Copyright 2001
American Chemical Society.
derivative is attributed to the chain topology and in particular to
the higher steric hindrance preventing aggregation of the
macromolecules.
Surface Activity. The discussion so far has been focused on
the CMC values. It must be mentioned how it has been reported
often to be independent of the absolute molecular weight of the
block copolymer (provided that the composition remains the
same).382,428 On the other hand, precisely such lack of
dependence can be used to illustrate the fact that the CMC
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values are often insufficient when trying to study the surface

activity of polymeric surfactants.
It is worth noticing that the determination of CMC for
macrosurfactants, especially for those known to give “frozen”
micelles, has been questioned.134 Given the very low CMC values
usually found for macrosurfactant, it has been proposed that the
technique of pyrene fluorescence (often used in these cases)
could give an artifact: the partition of pyrene between micelles
and water could be in favor of the water just because of the large
difference in concentration and not because of the dissociation of
micelles.
Dependence of Surface Activity on Molecular Weight. It is
possible to observe that in general polymeric surfactant, when
dissolved in water, causes a decrease in the corresponding surface
tension. This is normally attributed to a specific orientation of
these copolymers at the surface with hydrophobic block pointing
at the air side of the surface. However, the macromolecular
nature of the surfactant has direct consequences for the nature of
this behavior. Indeed, for the same copolymers mentioned Figure 24. Concentration dependence of the surface tension curves of
above,428 displaying the same CMC as a function of the average aqueous solutions of 35 with different PMMA block length: no PMMA
molecular weight, a clear dependence of the surface activity on (■); PMMA13 (⧫); PMMA25 (●); PMMA45 (▲); PMMA60 (*);
the same parameter (average molecular weight) is clearly random PMMA21 (○); and random PMMA53 (Δ). Reproduced with
permission from ref 181. Copyright 2011 Elsevier.
detected (Figure 23).
Dependence of Surface Activity on Chemical Structure. The
surface activity of a polymeric surfactant is sensitive to minor
changes in the block chemical structure. Antoun et al.261 were
able to illustrate this principle in a very elegant way. They studied
copolymers of MMA with 2-(dimethylamino)ethyl methacrylate
89, with the latter group being used as such or after
quaternization with ethyl (89b), pentyl (89e), or heptyl (89f)
groups. When comparing the corresponding surface tension in
water solution, relevant differences could be observed (Figure
25).

Figure 23. Critical micelle concentrations of PEO-PPO-PEO macro-

surfactants determined from the measurement of surface tensions: Mn =
1100 g/mol (■); Mn = 2000 g/mol (●); Mn = 2800 g/mol (▲).
Reproduced with permission from ref 428. Copyright 2002 Wiley.

Dependence of Surface Activity on Monomer Distribution.

Furthermore, the kind of copolymer (i.e., block vs random) has a
prominent influence on the corresponding surface activity. When
considering181 copolymers of sulfonated polystyrene (in the
form of their Na salt) and MMA 35, the surface tension curves of
the corresponding water solutions (Figure 24) are a clear
function of this parameter.
It is clear how the block copolymers (closed symbols) display
in general higher surface activity than the random ones (open
symbols) at comparable molecular weights. This has also been
demonstrated by Liu et al.248 using polymers 85−87. Polymer 87
(with a grafting ratio of 0.04, n = 8) has a lower CAC compared to
polymer 85 (with a grafting ratio of 1.02, n = 8). Even with the
higher grafting ratio (more hydrophobes), the block-like
distribution present in polymer 87 leads to a lower CAC
compared to the random distribution of the hydrophobes in
polymer 85.
8538
Figure 25. Concentration dependence of the surface tension of aqueous
solutions of the PMMA-b-PDMAEMA 15/85 diblock 89 non-
quaternized (Q0) and quaternized by different alkyl bromides: 89b
(Q2), 89e (Q5), and 89f (Q7). All the solutions are added with NaCl
(0.1 M). Reproduced with permission from ref 261. Copyright 2001
Elsevier.
In particular, quaternization by ethyl groups results in the
higher CMC and lowest surface activity. This can be explained by
a change of the conformation of the chains at the water−air
interface. Upon quaternization electrostatic repulsion is
generated, thus leading to a low degree of packing of the chains
at the interface. The general principle is that a decrease in the
charge density of the hydrophilic block results in lower CMC.
The differences with 89e and 89f are due to the formation of
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hydrophobic aggregates (of the alkyl groups) rendering the
situation more difficult. Indeed, such interaction, even at
relatively low concentration of the responsible groups, might
prevent migration of the polymeric chains toward the interface.64
This interplay between electrostatic interactions and hydro-
phobic ones is quite general and observed also in other systems.
Fischer et al.218 prepared copolymers of dimethylacrylamide
(DMA) with N-hexadecyl-4-vinylpyridinium bromide 53a. The
corresponding surface tension measurements (in a mixture of
solvents) are a clear function of the DMA block length as well as
its relative percentage, with an exact interpretation being
hindered by the use of a three-component mixture as solvent.
Another consequence of the macromolecular nature of
polymeric surfactants resides in anomalous micellization
behavior as well as in the corresponding surface activity. Indeed,
many systems are actually characterized by a so-called
“schizophrenic behaviour”,68,69,71,278,279 i.e., the presence of
normal micelles, inverse ones, and molecularly soluble species as
a function of slight changes in external parameters such as
temperature or pH (Figure 26).
Figure 26. Schematic schizophrenic behavior. Adapted with permission
from ref 67. Copyright 2001 Wiley.
In this case the block structure and length are considered to be
crucial in determining the copolymer solubility and thus its
behavior in water.429 To conclude the discussion on surface
activity and micellization of macrosurfactants, it is worth noticing
that the fundamental research in the field is still active. The
micellization dynamic and the mechanisms lying beneath are not
yet completely elucidated, and they might sensibly differ from
what is observed for low-molecular-weight surfactants.430 For
example, for some charged polymeric surfactants, the surface
activity decreases upon addition of salts, contrarily to what
happens for their low-molecular-weight counterparts.431
Several experiments show that in most cases the surface
activity of macrosurfactants is detectable only when the
hydrophobic block is sufficiently short (below 20 units in case
of 34, for example). More in general, it seems that, to display a
clearly measurable surface activity, the hydrophobilicity of the
insoluble block has to be moderate. This happens not only for
short blocks of highly hydrophobic mono-
mers96,191,254,255,258,262,301,431 but also for long blocks of
moderately hydrophobic monomers (such as DEGA)117 or
hydrophobic blocks in which a hydrophilic monomer (such as
8539
Review
AA136 or DMAEMA432) is randomly incorporated up to 50 mol
%.
4.1.2. Polysoaps. PAM-Derived Polysoaps. Two studies
investigated the association behavior of polymer 158 (R1 =
NIPAM, R2 = CH3) using fluorescence spectroscopy. Zhang et
al.345 demonstrated that the association degree (indicative for
surface activity) increases with the incorporation rate of the
hydrophobic group, and Li et al.433 observed a decrease in CAC
from 3.1 to 0.8 g/L as the incorporation rate of the hydrophobic
group increased from 0.06 to 0.88 mol %. One improvement for
the fluorescence studies is the fluorocarbon-substituted pyrene,
suggested by Li et al.433 The fluorocarbon-modified pyrene is
more informative for hydrophobic association given its better
affinity for the microdomains of the fluorocarbon-modified
amphiphilics. For polymer 158 (R1 = OH, R2 = CH3), the
decrease of the I1/I3 ratio is more pronounced as the
incorporation rate of the hydrophobic monomer is increased.55
Similarly, the CAC of polymer 158 (R1 = NIPAM, R2 = H)
decreases from 4.5 × 10−4 to 1.3 × 10−4 g/mL as the
incorporation rate of the hydrophobic monomer is increased
from 0.113 to 0.227 mol %.346 The interfacial tension decreases
upon increasing the incorporation rate, from 2 to 3 mol %, of the
hydrophobic monomer in polymer 148 (R1 = 2, R2 = H).65
However, the surface tension does not change significantly when
the incorporation rate is increased. The same trend is observed
for polymer 148 (R1 = 1, R2 = H) when the incorporation rate is
increased from 3 to 5 mol %.65,434 However, the comparison is
not completely sound given the fact that the molecular weights of
both polymers (148 [R1 = 1, R2 = H] and [R1 = 2, R1 = H]) are
not provided. Polymer 148 (R1 = 3, R2 = H) displays a much
lower IFT than polymers 148 [R1 = 1, R2 = H] and [R1 = 2, R2 =
H]; however, the comparison is not justified given the differences
in polymer composition, molecular weight, and polymer
concentration at which the IFTs were measured. Polymer 148
(R1 = 3, R2 = H) is prepared using the micellar copolymerization
technique,336 which yields a block-like distribution of the
hydrophobic monomers. Nevertheless, polymer 148 (R1 = 3,
R2 = H) is pivotal in that it was used to illustrate the relaxation
processes below and above the CAC.435 Below the CAC, two
relaxation processes exist, one (fast) related to the exchange of
hydrophobic microdomains between the proximal and distal
regions in the interface and another one (slow) related to the
conformational changes of the polymer backbone in the interface
(oil[octane]−water).435 Above the CAC only one relaxation
process exists, which is believed to be the associations formed by
hydrophobic macrodomains.435
In polymer 149 the hydrophobic groups are randomly
distributed as blocks (between 25 and 28 units). To determine
the onset of association, i.e., the CAC, nonradiative energy
transfer (NRET) studies are usually performed. Smith and
McCormick339 determined the CAC for polymer 149 (m = 8) to
be 0.1 g/dL (1000 ppm). A decrease in the CAC is observed
when the length of the hydrophobes is increased, i.e., the CAC
drops to 0.04 g/dL (400 ppm) when m = 10 in polymer 149.338 A
similar trend was observed for polymer 162, where the CAC
decreases from 0.05 (polymer 162, m = 7) to 0.025 wt %
(polymer 162, m = 11) with the increase in length of the
hydrophobe.353 One can argue that the CAC can be lowered
even further by using longer hydrophobes; however, this will lead
to insolubility as demonstrated by increasing the length of the
hydrophobes (polymer 149, m > 12).338
The water solubility of polymers 144 and 145 is dependent on
the incorporation rate of the hydrophobic (DEmMA) unit.
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Above an incorporation rate of 30 mol %, the polymers are not
water-soluble.334 The CMC of polymer 144 (m = 2) decreases
upon increasing the incorporation rate of the hydrophobic unit.
A similar behavior is observed for polymer 145 where m = 6 and
25. However, for polymers 144 (m = 2) and 145 (m = 6 and 25),
a minimum in the CMC is reached at incorporation rates of 7 and
10 mol %, respectively.329,334 Polymer 165 has a CMC of 0.6 g/L
(determined via the I1/I3 ratio), which decreases with increasing
incorporation of the hydrophobic groups (although the CMC of
the polymer containing the highest amount of hydrophobe is
provided).54 A decrease in the CMC of the copolymers of
NaAMPS/DEmMA (polymer 145) is observed when the
number of ethylene oxide (EO) units in the random polymers
is increased.62 In addition it was demonstrated that the
aggregation number (Nagg) of the C12Em (EO-containing)
moieties is similar (somewhat larger) to the values observed
for free C12Em surfactants where the number of EO units is 6 or
25.328,329,334 Similar results were obtained when NaAA (instead
of NaAMPS, polymer 144) was used as the charged moiety.62,329
For both polymers (144 and 145), it was demonstrated that the
CMCs of the polymers are between 10 and 100 times smaller
than the values for the discrete (DEmMA) surfactants.328
The CMC of polymer 146 decreases as the incorporation rate
of the hydrophobic moieties increases, which is in line with small
surfactants.63 The effect of the chain length (number of EO
units) on the CMC was not determined, although smaller
micelles are formed with longer side chains (more EO units).63
Polymer 163 displays the same trend, a decrease in CAC with an
increase in incorporation rate of the hydrophobic groups, as
investigated using fluorescence spectroscopy.354 Although the
exact CAC was not determined, the ratio between the intensities
of the first and third vibronic peaks (I1/I3 ratio) is lower for
polymer 163 (x = 1, y = 25, z = 0.1) compared to polymer 163 (x
= 0.5, y = 25, z = 0.1). In addition the inflection point of the curve
(I1/I3 ratio vs polymer concentration) occurs at a higher polymer
concentration for the latter polymer.
The effect of small differences in the chemistry of the
surfactant monomers is demonstrated with polymer 147. The
authors335 determined the CMC of the free surfactant monomers
(prior to incorporation into the copolymer) and observed that
the presence of an extra C2H5 group (R1 = C2H5) reduces the
CMC from 0.77 to 0.56 mM. Nevertheless, it remains difficult to
comment on the effect of the extra C2H5 group on the CMC of
the polymer without the actual measurement. Although Noda et
al.328 demonstrated that the CMCs of copolymers are between
10 and 100 times lower than the corresponding free surfactants,
the interactions between the extra C2H5 group with the polymer
backbone can give rise to an unexpected behavior. Zhang et al.345
demonstrated that the presence of an alkyl group can influence
the interfacial properties significantly. The decrease of the
intensity ratio of excimer to monomer (I550/I375) in fluorescence
experiments indicates the formation of aggregates. The decrease
of I550/I375 occurs at a much lower polymer concentration for
polymer 158 (R1 = NIPAM, R2 = CH3) compared to polymer
158 (R1 = NIPAM, R2 = H). The location of a charge on the
hydrophobic moiety also affects the surface activity of the
polymer. This was demonstrated by Morimoto et al.350 with
polymer 158; the amphiphilic with the charge closest to the
backbone (polymer 160, R = 1) displays the lowest CMC of the
two polymers. The molecular weight of the polymer also plays a
crucial role for the value of CAC, with higher molecular weights
displaying the lowest CAC. This was demonstrated with polymer
150 (random distribution of hydrophobic blocks) where the
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CAC decreases with increasing molecular weight.340 However,
surprisingly the block length and the incorporation rate of the
hydrophobic groups do not decrease the CAC.340 Polymer 148
(R1 = 3, R2 = COOH) has a CAC value of 0.5 g/dL, which is
comparable to polymer 149 (m = 8).337
The position of the hydrophobic groups is also an important
parameter that affects the CAC. This has been demonstrated
using polymers 151 through 157. Although the CAC was not
directly measured, the concentrations (Cη) at which the solution
viscosity departs from the values of the unmodified polymers
were measured. The theory of Einstein stipulates that the
solution viscosity (of a dispersion) in the dilute regime is
determined by the size of the particles (or aggregates). The
solution viscosity of a semidilute solution is determined by the
size of the particles and their interaction with one another. The
size of polymer particles is dependent on the molecular weight
and on their conformation. With the presence of hydrophobic
groups, the polymer coil can be smaller than the unmodified
polymer at the same molecular weight due to intramolecular
hydrophobic associations. This leads to a lowering of the critical
overlap concentration for the hydrophobically modified
polymers. Therefore, for polymers 151−157, the measured Cη
is dependent on the critical overlap concentration (C*) and the
CAC. Since aggregation occurs below the C*, the Cη is higher
than the corresponding CAC. This has been demonstrated for
associative polymers based on poly(ethylene oxide)
(PEO).245,248,253
The Cη decreases upon increasing the length of the
hydrophobic blocks in the telechelic polymer 152.343 The Cη
of polymer 151 (n = 7) is higher than that of polymer 152 (n =
15).341,342 The authors341 hypothesized that the length of the
hydrophobe is more important than hydrophobicity for
hydrophobic association to arise. However, when comparing
the multisticker [151 (n = 7) compared to 154 (m = 15)] and
combined polymers [155 (n = 7) compared to 156 (m = 15)],
the exact opposite is observed.341 The Cη of the combined
polymer 155 (n = 7) is the lowest compared to its telechelic [151
(n = 7)] and multisticker [153 (n = 7)] analogues.341 The
placement of the hydrophobic groups at the ends leads to a lower
Cη compared to randomly distributed (multisticker) along the
backbone or combined as demonstrated by comparing polymer
152 (m = 11 and 15) with polymer 153 (n = 5 and 7) and
polymer 157 (n = 5, m = 11),343,344 which can be seen as evidence
that the telechelic polymers are better surface-active agents than
multisticker ones. However, this comparison is not justified given
the difference in length of the hydrophobic groups (C16 and C12
compared to diC8 and diC6). A later study compared polymers
151, 153, and 154 (all with n = 7), and the Cη of the multisticker
polymer was the lowest, suggesting that multisticker polymers
are more surface-active that telechelic ones. However, the lengths
of the hydrophobic groups (although held constant for the
comparison) are just above the length below which no
hydrophobic associations arise.342,436 Therefore, it can be
concluded that to obtain a good surface-active agent the
placement of the hydrophobic groups is dependent on its nature
(length and chemistry). It was demonstrated by Yahaya et al.64
that the surface tension of the aqueous polymeric solution
containing polymer 148 (random copolymer) decreases as the
concentration of the polymer increases. The interfacial tension,
using n-decane−aqueous polymeric solutions, also displayed a
decrease with increasing polymer concentration. A small
decrease in the interfacial tension was also observed with
increasing salt (NaCl) concentration, up to 9 wt %. The same
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results (in terms of the trend) were obtained for polymer 148 (R1
= 2, R2 = H) (random copolymer).65 However, the decrease in
surface tension and interfacial tension (in the absence of salt) is
slightly more pronounced (lower values), indicating a more
surface-active agent. In the presence of salt, the exact opposite
behavior is observed where polymer 148 (R1 = 1, R2 = H) has a
lower interfacial tension. The surface activity of an aqueous
solution containing polymer 166 depends on the incorporation
rate of the 3-(N,N-diallyl-N-methylammonium)propane sulfo-
nate (DAMAPS) unit and on the pH of the solution. When the
incorporation rate of the DAMAPS is zero, the surface tension of
the solution decreases from 74 (pure water) to 55 mN/m2 as the
polymer concentration is increased to 1 g/dL at a pH of 4.60.
When the polymer concentration is increased to 0.65 g/dL at a
pH of 9.71, the surface tension decreased to 33 mN/m2.
According to the authors,356 as the ionization degree is
decreased, the effective hydrophobic content of the polymer
increases and thus hydrophobic interactions arise. Similar results
are obtained when the incorporation rate of the DAMAPS unit is
44 mol %. However the decrease in surface tension with the
increase in pH is not as pronounced. The difference is attributed
to the high hydrophilicity of the groups even at low ionization
degrees.356
The interfacial properties of polymer 161 are slightly
dependent on the presence of electrolyte (NaCl).351 The I1/I3
ratio reaches the hydrophobic limit at a lower polymer
concentration in the presence of electrolyte (0.10 instead of
0.15 wt %). This indicates that the hydrophobic associations arise
at a lower polymer concentration in salt solutions. Feng et al.353
noticed that the addition of NaCl leads to a reduction in the I1/I3
ratio of an aqueous solution containing polymer 162 (m = 7).
Similar results were obtained with polymer 164. Both
studies353,355 attributed the results to the stronger hydrophobic
interactions caused by the presence of salt. The surface tension of
an aqueous solution containing polymer 161 decreases as the
concentration increases and displays a minimum (in the low-
concentration region) at a concentration of 0.15 wt %. The
lowest IFT is observed at the same polymer concentration (in an
n-decane−water solution).351
The dynamic surface properties of polymer 159 have been
investigated by Kopperud and Hansen.347 They demonstrated
that all the amphiphilic polymers investigated display surface
activity. However, the adsorption rate of the polymers to the
surface layer is low. The authors347 hypothesized that the
adsorption is controlled by unfolding and reconfiguration of the
bulk polymer and the penetration of the surface layer by
individual hydrophobic blocks. A decrease in the adsorption rate
is observed when the molecular weight is increased and when the
block length of the hydrophobes (maintaining a constant
hydrophobe content) is increased. However, higher hydrophobe
contents (maintaining a constant hydrophobe length) lead to
higher adsorption rates.
HEUR. The association behavior of polymer 77 was
investigated using fluorescence spectroscopy. The emission
intensity increases when hydrophobic associations arise,
indicating the formation of micellar aggregations. Increasing
the length of the hydrophobes, i.e., the hydrophobicity, leads to
aggregation being formed at lower concentrations.242 This was
demonstrated with polymer 84 where the CAC decreases from 5
× 10−2 to 1 × 10−4 g/mL when an octadecyl is used as the
hydrophobic group instead of dodecyl.248 The linking group also
affects the CAC in that the more hydrophobic (H12MDI [a] is
more hydrophobic than HDI [b]) it is, the lower is the CAC.242
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Review
Although the studies243,244 did not measure the differences in
CAC, the same trend is expected when comparing polymer 78
with 79. The combination of the hexadecyl end group and the
isophorone diurethane (IPDU) linking group has a higher
hydrophobicity compared to the hexadecyl group only. Similar
results were obtained when polymer 80 (x = 304) was compared
with polymer 81 (x = 304). The subtle difference in the linking
group has a pronounced effect on the CAC. Polymer 80 (x =
304) possessing ether linkages has a CAC of 8.5 × 10−5 M,
whereas polymer 81 (urethane linkage, x = 304) has a CAC of 2.5
× 10−5 M.246 Even polymers functionalized at only one end
display the same difference. The CMC of polymer 82 (R = C8F17,
x = 120) is 20 times lower than the CMC of polymer 83.252
The molecular weights of the polymers also affect the CMC in
aqueous solution, as demonstrated with one-ended fluorocarbon
polymers 83. Increasing the molecular weight by a factor of 2
(from 5 to 10 kDa) results in an increase of the CMC from 1.5 to
7.0 × 10−6 M.251 The same trend is observed for the polymer
series 80 (x = 227, 454, or 795). The CAC increases from 1.5 to
10 g/L upon increasing the molecular weight of the polymer
from 10 to 35 kDa.245 The CAC of polymer 81 (n = 12) increases
from 2 × 10−3 to 7 × 10−3 g/mL as the molecular weight
increases from 12 to 20 kDa.248 In addition, it is expected that the
PDI of the polymers also affects the CAC. The low-PDI polymers
can associate more readily than polydisperse polymers and thus
display the lowest CAC values.242
Alami et al.249 compared the micellization behavior of polymer
81 (x = 454) to that of two different low-molecular-weight
surfactants (ionic SDS and nonionic C12E6) using fluorescence
spectroscopy. The I1 /I3 ratio decreases over a narrow
concentration range for the two lower-molecular-weight
surfactants, while for polymer 81 (x = 454) it decreases over a
much wider concentration range. Therefore, it is difficult to
assign a CMC for the polymer. Nevertheless, the authors249
define a CMC close to the inflection point of the curve. The
CMCs of SDS and C12E6 are both also close to the inflection
point of the corresponding curve. The CMC of the polymer, 7.5
× 10−4 M, lies between those of the ionic and nonionic
surfactants. Similar results, a decrease of I1/I3 over a wide
concentration range, were obtained when comparing polymers
85−87. The CAC was defined close to the aforementioned
inflection point of the curve, with the values decreasing when n
(length of the hydrophobes, polymers 85−87) is increased (i.e.,
the hydrophobicity). Increasing the grafting density also leads to
a decrease in the CAC.248 Also noteworthy is the fact that the
concentration range over which the decrease of the I1/I3 is
observed increases with an increase in n.248 In this case relatively
lower molecular weight seems to result in better surface activity
(i.e., lower surface tension of the corresponding water solution).
Polysaccharides. Because of the large availability and the
relative simplicity of the functionalization procedures, several
naturally occurring water-soluble polysaccharides have been used
as starting materials for the synthesis of polymeric surfactants. As
described in section 3.2.2, the addition of the hydrophobic
groups is generally carried out in conditions that afford polymers
with a random distribution of the modifying moieties. The
resulting hydrophobically modified polysaccharides can be
included in most cases in the class of polysoaps. Many polymeric
surfactants have been reported to have good emulsification and
dispersion abilities but give only a moderate reduction of surface
and interfacial tension.437 Hydrophobically modified polysac-
charides are not an exception.The literature on hydrophobically
modified dextrans with molecular weights up to 100 000 Da and
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with a degree of substitution (DS) up to 0.2, as summarized by
Rotureau et al.,362 shows that there is little influence of the nature
of the hydrophobic group and the DS on the CMC, which is
generally in the range of 1−2 g/L (10−5−10−6 mol/L). On the
other hand, the surface activity above the CMC decreases
sensibly by increasing the DS. Similar or slightly lower values and
the same trend have been observed for other studied
polysaccharides such as hydroxyethylcellulose,357−360 carbox-
ymethylcellulose, 361 carboxymethylpullulan,366,367 and pec-
tin;370 therefore, it seems to be quite general. Comparable
values of CMC (expressed in mol/L) have been found also for
hydrophobically modified pectin with a low molecular weight
(∼4000 Da) 368 and for a dextran functionalized with relatively
long PLA-insoluble chains, which can be considered more like a
comb polymer. 372 Regardless of the structure, the decrease of
surface tension is generally moderate, with typical values being
around 45−55 mN/m and in any case not less than 30 mN/m.
However, stable O/W emulsions are formed for many of the
studied systems.361,363−365,368,438−441 The rheological properties
of these polymeric surfactants, which show gelation proper-
ties,327 seem to play an important role in the emulsion
stability.371,438 To our knowledge, no systematic study
concerning the dependence of surface activity on the molecular
weight of the polymer has been reported yet. The adsorption of
hydrophobically modified polysaccharides at the air/water as
well as at the oil/water interface is generally slow, so a gradual
decrease with time of the surface/interface activity to an
equilibrium value is often observed with these systems. Dynamic
surface activity measurements have been carried out in some
cases.358,362,371 A higher degree of hydrophobic substitution361
or the presence of a charged substituent362 seem to accelerate the
adsorption process. The adsorption of the polymeric surfactant is
considered to be a diffusion-controlled process at short times,
with negligible desorption and no interaction between adsorbed
and adsorbing macromolecules, while for longer times the
process is better described as a Langmuir isotherm.362 Some
proposed mechanisms also take into account a barrier effect or
reorientation/rearrangement of the polymer at the surface.358,362
In the case of a hydrophobically modified chitosan, various stages
of adsorption and folding/unfolding of the polymer have been
proposed to explain the presence of lag times in the dynamic
surface tension and some rheological data (Figure 27). 371
4.2. Rheology of Macrosurfactants
Despite the large amount of publications concerning synthesis
and self-assembly of amphiphilic copolymers, the rheology of
these systems has not been extensively investigated so far. The
Figure 27. Schematic representation of different stages of the alkylated
chitosan adsorption. Adapted with permission from ref 371. Copyright
2005 Elsevier.
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Review
most studied systems are AB diblock and ABA or ABC triblock
(telechelic) copolymer in which the hydrophilic block B is
constituted by PEO or PAA and the hydrophobic blocks are
constituted by polystyrene or aliphatic alkyl chains.442−444
These kinds of polymers form viscoelastic solutions that
present a transition to gels at a certain critical concentration,
depending on the composition and the architecture of the
polymer. Polymers containing a polyelectrolyte chain such as
PAA are of particular interest because the presence of Columbic
interactions leads to highly stretched conformations in solution,
which causes a dramatic increase in moduli and viscosity at
relatively low concentrations and an unusual rheological
behavior. Moreover, the charge density and the extent of ionic
interactions are dependent on pH and ionic strength, and
consequently, the rheology can be tuned by acting on these
parameters. A deep study of the rheology of telechelic ABA and
ABC copolymers with a charged PAA or PMAA hydrophilic
middle block has been performed by Tsitsilianis and co-
workers.147−150,445 In this case the two associative blocks can
assemble either into the same core, forming “flower-like”
micelles, or into different cores, forming bridges and thus a gel
via formation of transient networks (Figure 28), depending on
the concentration and the compatibility of the hydrophobic
blocks.150 A PS-PAA-PnBA (PnBA = poly(n-butyl acrylate))
triblock copolymer 16 shows a similar viscosity profile to the
analogous PS-PAA-PS system 15 (Figure 29) but a lot higher
absolute values of viscosity and yield stress at the same
concentration.150 According to the authors, the incompatibility
between the PS and the PnBA blocks would favor the
intermolecular aggregation over the intermolecular one, explain-
ing the observed behavior.
When the hydrophilic block is constituted by a charged
polyelectrolyte, it is expected to have an extended conformation
in water due to repulsive electrostatic interactions. As a
consequence, 15 exhibits a gel concentration about 1 order of
magnitude lower than that of the latter PEO derivative in which
the middle block has comparable length. 148 A viscosity/
concentration profile similar to that of 15 was observed for a
MMA-b-DMAEMA-b-MMA telechelic copolymer 91 but,
remarkably, direct observation of the micellar structure by
means of atomic force microscopy (AFM) microscopy reveals
the absence of “loops”. This has been attributed to the shortness
of the DMEAMA middle block.265
Diblock copolymer aggregates in solution are normally
constituted by a dense rigid core surrounded by a hydrophilic
corona. The rheological properties of these polymers are
determined by the interactions between the coronas, but little
is known about the interaction mechanism.446 Anyway, at
sufficiently high concentrations the micelles are jammed and the
solution stops flowing, forming a viscoelastic gel.444 A relatively
short PS20-PAA85 polymer 1 has been studied by Korobko et
al.446 It exhibits a Newtonian plateau at low shear in a large
interval of concentrations and shear thinning at high
concentrations. Also in this case, the zero shear viscosity
increases dramatically with polymer concentration, from 1−4
orders of magnitude greater than water. Addition of salt (1 M
KBr) yields solutions with a zero shear viscosity comparable to
that of water. This behavior is explained in terms of chain collapse
due to shielding effects, with a consequent weaker interaction
between the micelles.443,446
If hydrophobic groups are present in the polyelectrolyte block
they can act as “stickers”, favoring the gelation of the system
(Figure 30).443 PS-b-(AA-co-EA) copolymers show a decrease in
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Figure 28. Schematic representation of the gelation mechanism of 16/water system. Reproduced with permission from ref 150. Copyright 2005
American Chemical Society.

Figure 29. Double-logarithmic plots of shear viscosity at (γ = 1 s−1) for PS-PAA-PS (left) and zero shear viscosity for PS-PAA-PnBA (right) versus
concentration. Adapted with permission from refs 148 and 150. Copyright 2000 and 2005 American Chemical Society.

in the literature where the dependence of the rheological

Figure 30. PS-PAA micelles associated via ethyl acrylate stickers in the
PAA block. Reproduced with permission from ref 443. Copyright 2006
American Chemical Society.
the gelation concentration and an increase in viscosity and elastic
moduli by increasing the amount of EA groups scattered along
the AA block.443
Raffa et al. investigated the rheology of a diblock 18, a triblock
33, and a four-arm block star 180 PS-b-PMAA copolymer
prepared by ATRP.85 This work is one of the very few examples
8543
properties from the molecular architecture of block polyelec-
trolytes is the subject of the study. Rheology of star PAA
polymers capped with short PS ends also has been studied.99,447
Also these polymers form elastic gels in water at a relatively low
concentration (∼2.2 wt %).99 As for other PAA-based
copolymers, a drop in viscosity is observed upon addition of
salt (0.1−0.9 M NaCl), but the system still presents the
characteristic of a gel, showing that the polyelectrolyte screening
upon salt addition shrunk the PAA chains but did not affect the
hydrophobic association.99 The authors compared their findings
with other results published by other groups for analogous linear
systems. Elastic moduli of the studied star polymers are
comparable with those of diblock PS-PAA 1 and triblock PS-
PAA-PS 15 copolymers, but the gelation concentration is
sensibly higher. This difference can be attributed to the different
topology, as starlike polymers are likely to have a smaller
hydrodynamic radius than a corresponding linear one, but the
longer length of the hydrophobic blocks and the higher
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molecular weight of the linear polymer make the two systems
difficult to compare.99 When a linear PS-PAA-PS 15 copolymer
with comparable PS end blocks length and PS/PAA ratio is
considered, the star polymer results in more effective network
formation and gel with higher elasticity.447
The solutions of polymers with longer PS ends form gels
characterized by short linear viscoelastic region, more
pronounced shear thinning, and less marked gel softening with
temperature. This behavior is rationalized by the authors
considering that longer PS chains lead to stronger hydrophobic
association. 447
Besides application as emulsion stabilizers, polymeric
surfactants have been also claimed in other fields. In particular,
the presence of hydrophobic blocks renders these materials
suitable as viscosity modifiers.131 In this case the same
hydrophobic interactions responsible for the surface activity
and micellization behavior are also the cause for the increased
viscosity. Colinet et al.,448 when studying graft copolymers of CL
onto alginates, pointed out the fact that these two effects are
actually coupled with each other simply because of a common
origin. Indeed, when looking at viscosity as a function of the
grafting efficiency (Figure 31a), a clear trend is detectable for
both PCL average molecular weights.
Figure 31. Intrinsic viscosity (a) and critical overlap concentration (CCr)
(b) for PCL-grafted alginates. Data reproduced with permission from ref
448. Copyright 2009 Elsevier.
In both cases the decrease of [η] with the grafting efficiency
can be attributed to the screening of the electrostatic repulsion of
the alginate precursor as well as to the increased chance of
hydrophobic interactions with the increasing number of available
PCL chains. Indeed, the observed trend is practically mirrored by
the one of the critical overlap concentration (CCr) as a function of
the same grafting efficiency. In a semidilute regime, as the one
presently used, such concentration is indicative of the CMC and
is also a function of the interaction forces present in the system.
The underlying concept here is that the same two factors
promoting association (i.e., screening of the electrostatic
repulsion between the backbone as well as favored hydrophobic
interactions) are also responsible for the decreased viscosity.
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Review
The close relationship between hydrophobic interactions and
viscosity of the corresponding water solution has been recently
reviewed.327 For the present paper it suffices to underline the
general trend, i.e., an increase in the absolute viscosity as a
function of the salt concentration, as the one measured for
copolymers of acrylamide and styrene of the polysoap type 161
(Figure 32).351
Figure 32. Viscosity of a 2% solution of 161 as a function of NaCl
concentration at three different shear rates. Reproduced with permission
from ref 351. Copyright 1999 Wiley.
As the salt concentration increases, hydrophobic interactions
become stronger, which renders the apparent viscosity higher
than in the case where no salt is present. The same kind of parallel
dependence (of aggregation and viscosity) can be found as a
function of the polymer topology.96
Besides direct correlation, also conceptual discrepancies are
observed. Indeed, Eghbali et al.125 prepared copolymers of butyl
acrylate and acryclic acid 3. They measured surface tension and
viscosity of the corresponding water solutions as a function of the
pH. The latter has a direct influence on the ionization of the
−COOH groups (of the AA block) and thus on the ionization
degree (α), defined as the fraction of −COOH groups ionized at
a given pH. While the surface tension did not change as a
function of the pH, the solution viscosity shows the presence of a
maximum (Figure 33).
The authors were able to explain this behavior by assuming
that, at about α = 0.5, corresponding to the maximum position in
Figure 33, the polymeric chains are already fully stretched in
water solution and that a further increase in the amount of NaOH
(and thus in pH and α values) does not result in any
conformational (and thus viscosity) change. A maximum in
viscosity, this time as a function of temperature (Figure 34), also
has been observed for copolymers of caprolactone (CL) and
ethylene oxide (EO).449
Such a maximum is attributed in this case to a sol−gel−sol
transition, which can take place at relatively high concentration.
It is also interesting to notice how an increase in the CL block
length, going from (a) to (c), results in a lower onset for the
maximum. This suggests once more the close relationship
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Figure 33. Zero shear viscosity of a 0.5% solution of 3 as a function of α.
Reproduced with permission from ref 125. Copyright 2006 American
Chemical Society.
Figure 34. Viscosity vs temperature curves for different diblock
copolymers at 20 wt % concentration: (a) E17C24, (b) E17C21, and (c)
E17C16. Reproduced with permission from ref 449. Copyright 2006
Wiley.
between hydrophobic interactions (or associative behavior) and
the rheological properties.
5. LINKS BETWEEN PROPERTIES AND APPLICATIONS
OF POLYMERIC SURFACTANTS
As already mentioned in the Introduction, the applications of
polymeric surfactants are widespread. They have been
extensively discussed in books and reviews; thus, the main
purpose of this section will be to outline the correlation between
physical properties of the polymeric surfactants and their
applications. For a detailed description of the polymer actually
used for a given application, the reader will be referred to
previous literature.
The most studied systems from the point of view of the
applications are block copolymers (di- and triblocks, mostly),
where the hydrophilic moiety is constituted by PEO and the
hydrophobic one is PPO, PBO, or, more rarely, styrene. These
kinds of polymeric surfactants (which include the commercially
available Pluronic and Synperonic series) have been extensively
employed as dispersants and an emulsion stabilizer and can be
found in formulations for detergents, dyestuffs, paints, coatings,
agrochemicals, ceramics, printing inks, etc.
8545
Review
Application of polymeric surfactants in gene and drug delivery
is becoming very popular. These and related applications are
based on the dependence of the hydrophilicity of some moieties
on external parameters (such as temperature, pH, and ionic
strength). This can induce the controlled formation and
disruption of micelles when the polymeric aggregate experiences
some change in such parameters when introduced in a living
system and in particular conditions. This topic is extensively
covered in many recent reviews,13,35,40,71 and it will not be further
discussed here.
The importance of polymeric surfactants for many applica-
tions can be seen in the fact that in many cases both rheology and
surface properties play a relevant role in this respect. In turn,
these features are directly related to the chemical composition
and the structure of the polymer. We will analyze these aspects in
more detail for what concerns emulsion stabilization, coating,
and oil recovery, categories which include most of the known
industrial applications of polymeric surfactants. Even if this
aspect will not be treated here, it is important to note that the
stimuli-responsivity of some of these polymers allows the
preparation of smart emulsifier, smart coatings, and so on,
greatly improving the applicative possibilities for these classes of
materials.35
5.1. Emulsion Stabilization
One of the main applications of polymeric surfactant is the use as
stabilizers in emulsion polymerization.16,19,22,97,116,123,192,450 In
this context they are believed to act as stabilizers (probably via a
steric repulsion mechanism) against coalescence122,183 and
Ostwald ripening.259 They also decrease the interfacial tension
between the two phases.451,452 Moreover, their chemical
composition determines the emulsion structure according to
the Bancroft rule in a way comparable to classic low-molecular-
weight surfactants.388 However, a main difference with their low-
molecular-weight counterparts is the fact that the behavior of the
polymeric surfactant can hardly be predicted by the hydrophilic−
lipophilic balance (HLB).453
For the polymeric surfactants to be active in their action, they
have to be adsorbed at the interface between water and the apolar
medium. In this respect the adsorption process is clearly
influenced by the same factors outlined above for the surface
tension at the water/air interface, i.e., pH,117,125,191,239,277,454,455
block structure and length,325,456,457 concentration,428 and
topology.96
The block length is in many cases crucial in determining the
adsorption at the interface. Indeed, when considering polymeric
compounds, one has to consider the folding of the chains at the
relevant side of the interface. Gref et al.228 illustrated this for
copolymers of P(EG-b-LA) (Figure 35).
When increasing the relative PLA (hydrophobic) block length
with respect to the PEG (hydrophilic) one, the former chains
assume a more sparse conformation at the interface, thus
factually limiting the adsorption at the interface. The situation is
even more complicated if one takes into account the influence of
the chain topology (and related steric hindrance) on the
adsorption.89,378,379,458 In particular the difference between block
and graft copolymers often results in different chain topologies at
the interface and thus different stabilization mechanisms via
steric repulsion. Exerowa et al.459 illustrated this (Figure 36),
although by using different materials.
The difference in chain topology at the interface has a clear
importance in determining the stability of the emulsion. Indeed,
the CAC (critical aggregation concentration) is again a function
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Figure 35. Scheme illustrating the hydrophobic PLA block length on the
density of filling of surfactant molecules at the oil/water interface.
Reproduced with permission from ref 228. Copyright 1998 Elsevier.
Figure 36. Schematic representation of conformation of triblock (left)
and graft (right) copolymeric surfactants at oil/water interface. The
situation when the oil droplets approach to a separation distance h that is
smaller than twice the adsorbed layer thickness δ is illustrated also.
Adapted with permission from ref 459. Copyright 2009 Elsevier.
of chemical composition, topology, and (in this case) not of the
molecular weight (F108 = 14.000 EO128PO54EO128, P104 =
5.900 EO31PO54EO31). In many cases graft copolymers have
been considered as more effective than block ones (of
comparable average molecular weight).395 This has been
attributed (Figure 37) to a different adsorption of the copolymer
at the interface.
Such dependence of the surface activity with the chain
topology is quite general if one excludes the special case of
polysoaps.392 The reason for such a discrepancy from the general
behavior is not discussed in the corresponding paper, even if it is
worth remarking on the fundamental difference in chemical
structure between block copolymers and polysoaps as a possible
reason.
8546
Review
Figure 37. Adsorption at the interface for block and graft copolymers.
Adapted with permission from ref 395. Copyright 2006 American
Chemical Society.
A classical example of structure−properties relationship is
given by the use of Pluronic polymers as emulsifiers: triblock
PEO-b-PPO-b-PEO are more suitable for O/W emulsion,
whereas for W/O emulsions PPO-b-PEO-b-PPO are preferred.
Moreover, systematic studies proved that there are optimums in
molecular weight and HLB, which affect important parameters
like interfacial tension, partition coefficient, thickness of the
adsorbed layer, and steric stabilization.18,29 Also rheology plays a
relevant role in emulsion stabilization. Because of the differences
in density, the dispersed phase can migrate under the action of
gravity to the top (creaming) or the bottom (sedimentation) of
the dispersing phase. This phenomenon can be described by the
Stokes equation ( eq 1),
2Δρgr 2
v=
9η0 (1)
where v is the droplet velocity, Δρ is the difference in density, g is
the gravity acceleration, r is the droplet radius, and η0 is the
viscosity of the medium. From the equation it can be seen that
the segregation can be steered by increasing the medium phase
viscosity (water). A polymeric surfactant acting at the same time
as a solution thickener and as a surface-active system represents a
successful choice for this kind of application.
The same principles apply to emulsion and or dispersion
polymerization. The use of polymeric surfactant in emulsion
polymerization is also well-established and has been reviewed,
also recently.16,18,19,22,122 The compatibility between the hydro-
phobic block and the forming latex particles seem to play a crucial
role in the quality of the formed material.307
5.2. Coatings
Polymeric surfactants often have been envisaged as suitable
materials for applications in the coatings and paints indus-
try.4,7,16,18,21,33−35,37,48,460 However, the analysis of the literature
shows that the claimed use of polymeric surfactants for industrial
coatings and paints formulations is in most cases only potential
and rarely actual. Again, the interest of using polymeric
surfactants for such applications originates from the importance
of both rheology and surface properties of the required materials.
Important phenomena for coating such as coalescence, wetting,
sagging, and leveling are governed by viscosity, yield stress, non-
Newtonian behavior, elasticity, and surface tension. For example,
leveling of a sinusoidal surface has been modeled, and the
leveling speed tv has been expressed as
16π 4h3γ ⎛ at ⎞
tv = ln⎜ ⎟
3λ 3η ⎝ a0 ⎠ (2)
where h is the average thickness of the coating layer, λ is the
wavelength, at and a0 are, respectively, the final and initial
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amplitudes, γ is the surface tension, and η is the viscosity at low
shear rate (the zero-shear viscosity is often used).461 It can be
noted here that, to achieve good leveling, high surface tension
and low viscosity are optimal. On the other hand, good
coalencence is given by low surface tension and sagging is
prevented by high viscosity. Thus, it is not easy to predict
theoretically the best system to be used for a desired coating.
5.3. Oil Recovery
The potential of amphiphilic polymers for enhanced oil recovery
(EOR) has been recognized, mainly because of their ability to
form shear-dependent transient association in water with
subsequent solution thickening at high salt concentrations and
in extensional flow.7,57,462 Surprisingly, less attention has been
paid to emulsification and surface properties of such polymers,
which is also a crucial parameter for EOR. In fact, such polymeric
systems are usually employed in combination with surfactants
and alkaline compoundsthe so-called surfactant−polymer
(SP) and alkaline−surfactant−polymer (ASP) formulationsin
which the polymer is added only to increase the viscosity of the
water, employed as a displacing fluid, while the other
components act as emulsifiers. Polymers proposed as solution
thickeners have been reviewed recently.327
Chemical methods for EOR consist of the injection of a
displacing fluid in oil reservoirs, in order to mobilize the crude oil
adsorbed in the porous rocks. The displacing fluid is generally
constituted by a dilute water solution containing an inorganic
base, a surfactant, a water-soluble polymer, or combinations of
these three components.463,464 The scope of the base (generally a
hydroxide as NaOH or a carbonate) is the same as the surfactant,
which is to decrease the interfacial tension between water and oil
phases. Indeed, the base reacts with the organic acid components
of the crude oil, forming a surfactant in situ.464 Polymer flooding
for EOR has been extensively studied.327 The mechanism of
enhanced recovery is generally explained in terms of decreasing
the mobility difference between injected and in-place reservoir
fluids to reduce channeling effects. The displacing phase should
have mobility equal to or lower than the mobility of the oil
phase.56,465 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. Because 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 weights,
resistance to mechanical degradation in shear, and complete
solubility in water.
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.466,467 The dimensionless ratio between the
viscous-to-capillary forces is called the 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.468,469 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.470 In this case we have
8547
Review
ΔP·k
Ca =
γ (3)
where ΔP is the gradient pressure, γ 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
v ·ηc
Ca =
γ (4)
where ηc is the viscosity of the continuous phase and v is the
Darcy velocity. Other formulations of Ca have been proposed
that 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 on the order of magnitude of
10−8−10−7 It is generally assumed that for a substantial increase
in oil production the Ca values should be increased by 2−3
orders of magnitude, meaning that surfactants should be able to
give ultralow values of γ (γ ≤ 10−2 mN/m).471−473
The use of polymeric surfactants could represent a favorable
option because 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 the Ca. Moreover, 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.469,474,475
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 completely absent surface
activity.117,133,143,185,194,205,287 This lack of surface activity is
usually explained with a very slow equilibration of polymeric
surfactant micelles (the so-called “frozen” micelles) that prevents
the possibility of the macromolecules to migrate to the interfaces.
As clearly documented by literature, the structure and the
composition of amphiphilic polymers are fundamental to
determine surface properties and rheology of their aqueous
solutions (vide supra). Moreover, the physical properties and
behavior can be greatly affected by pH, temperature, presence of
dissolved salts, and kind of flow. This review will be focused on
the synthesis and the properties of polymeric surfactants from
the point of view of their capability to increase the viscosity of the
water phase and to effectively lower the interfacial tension at the
water/oil interface. These systems are, at least in principle, more
suitable for potential EOR applications.
The idea to use polymeric surfactants for EOR, which can in
principle act either as solution thickeners or as 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
reviewed327) can in principle also act as surfactants, even if the
surface activity of such systems is usually not considered in the
studies. 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 the rock−water
interface, which can result in the loss of surfactant to reservoir
rock surface by adsorption,476 or to the incompatibility between
surfactant and polymer, resulting in the decline of polymer
properties such as aggregation, adsorption, and diffusion
performance in porous medium.477 Moreover, even if ASP
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flooding has proven to successfully increase oil recovery in the
field, the presence of the strong alkali has detrimental effects on
polymer performance, and in many cases additional polymer is
required to achieve the desired viscosity.474 Nevertheless, it is
believed that the alkali positively affects the process by reacting
with the organic acids present in the crude oil to form an in situ
surfactant and reduces the surfactant adsorption on the sand
surface, due to electrostatic repulsion between negatively
charged systems.
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.478 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 uses 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
questioned recently.479 Some very recent SP flooding experi-
ments480 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 ultralow values.
Several papers37,64,96,99,117,146,153,199,218,351,424,460,481−484 pro-
pose various amphiphilic polymers as systems for EOR. Despite
this, only a few studies concern 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.
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.354 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.477
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 amount
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 amounts 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.65
The nature of the hydrophobic groups seems to play a crucial
role in interfacial activity. A multiblock copolymer of AM with
styrene,351 phenylAM,434 and benzylAM64 showed different
surface behavior. Apparently, the higher the conformational
freedom of the monomer (PhenethylAM > benzylAM >
8548
Review
phenylAM > sty), the lower is the interfacial activity. This can
be explained in terms of rearrangements at the interfaces: the
longer hydrophobic spacer gives more freedom to the hydro-
phobes to extend away from the aqueous phase without causing a
significant change in the conformation of the copolymer.65 All
these AM-based polymers showed interesting salt effects:
viscosity and interfacial activity in the presence of added NaCl
are unaffected or in some cases improved. Their properties make
these polymers of potential interest for oil recovery.
6. CONCLUSIONS
Polymeric surfactants, i.e., macromolecular chemicals displaying
the presence of hydrophilic and hydrophobic moieties, represent
a relatively new class of chemicals characterized by a wide range
of application fields. These range from classical (e.g., as stabilizers
for emulsions) to relatively new ones (e.g., as thickeners for
EOR). The reason for such versatility resides basically in the fact
that in many aspects polymeric surfactants closely resemble their
low-molecular-weight counterparts. For example, they still
behave as surfactants in that they lower the interfacial tension
between water and an apolar phase. However, the polymeric
character of these materials confers to them additional
properties. In this respect the steric stabilization of dispersed
systems, the possibility of finely tuning the aggregation behavior
as a function of external stimuli, and the use of topology to
modulate the surface activity represent just paradigmatic
examples of these advantages.
Many scientific challenges remain open for a full under-
standing of the behavior of these materials and in particular in the
structure−property relationship. The HLB theory, allowing
reliable prediction for low-molecular-weight surfactants, in
general does not apply to polymeric materials. Along the same
line, the relationship between the aggregation behavior and the
rheological one is in many cases strongly dependent on the
studied system, thus hindering the establishment of general
principles. Furthermore, theoretical aspects bridging the “gap”
between different chemical structures are still lacking. This makes
it almost impossible at the moment to choose a priori a given
system for a given application.
Application of polymeric surfactant has been so far hampered
by the laborious and costly synthetic methods. Although the
situation is in this respect still difficult to predict, the use of
modern copolymerization techniques (such as ATRP and
RAFT) described in the present work in a detailed way allow
for envisaging a bright future for these materials.
From an application perspective and particularly in the general
field of EOR, several points are worth noticing. A clear, generally
valid and undisputed proof of the added values of polymeric
surfactant for EOR should be provided. In this respect one
should be able to correctly identify the correct reference
conditions. In the first instance, the alternative process (e.g.,
polymer or polymer−surfactant flooding) should be identified.
Second, the use of the corresponding reference system (i.e.,
polymer or polymer and surfactant) should be correctly defined.
The use of an alternative, although simpler chemical solution
(e.g., glycerin solutions for polymer flooding)485 severely
restricts, in our opinion, the generality of the obtained results.
To provide a general proof (vide supra), one should be able to
prepare polymeric materials in which the thickening effect
(mostly related to the average molecular weight and its
distribution) and the surface properties can be independently
varied. To the best of our knowledge, the only option available
for the product designer in this context is constituted by
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controlled radical polymerization methods, which, however, have

been limited so far (especially for water-soluble polymers with
different topologies) to mostly academic studies. The application
of these relatively new synthetic methods should then be studied
in terms of scaling possibilities.
A clear and generally valid relationship between the chemical
structure of the polymer and its properties in water solution (i.e.,
viscosity and surface tension) should be established. This is
essential for the design of new polymeric materials with tailored
properties linked to different oil well situations. Such a
relationship should also take into account the peculiar associative
behavior of macromolecular surfactant as opposed to their low-
molecular-weight counterparts. Indeed, the macromolecular Diego Armando Zakarias Wever (d.a.z.Wever@rug.nl) was born in
association is not only related to the thickening effect but also,
Oranjestad, Aruba, in 1984. He studied chemistry and chemical
and perhaps most importantly, to the surface activity. The lack of
such activity for some of the reported structures constitutes a engineering at the University of Groningen. He received his M.Sc.
clear distinction point (with respect to low-molecular-weight Degree in 2009 in the field of Chemical Engineering−Product
surfactants) and is indicative of a peculiar force balance in the
corresponding water solutions. This should constitute the Technology. He then started Ph.D. research on new polymers for
starting point of a (predictive) model, yet to be investigated. enhanced oil recovery under guidance from Prof. A. A. Broekhuis and

AUTHOR INFORMATION Prof. F. Picchioni, and he received his Ph.D. degree in 2013. As of

Corresponding Author October 2013 he is employed at Shell Global Solution International, and
*E-mail: a.a.Broekhuis@rug.nl. Phone: +31 (0)50 363 4918. Fax: he is working in the field of enhanced oil recovery.
+31 (0)50 363 4479.
Notes
The authors declare no competing financial interest.
Biographies

Francesco Picchioni (f.picchioni@rug.nl) was born in Terni, Italy, in

1971. He studied chemistry at the University of Pisa (Italy). He received

his M.Sc. degree in 1996 in the field of Polymer Chemistry. He then

Patrizio Raffa (p.raffa@rug.nl) was born in Pescara, Italy, in 1978. He started Ph.D. research on thermoplastic elastomers under the guidance
obtained his Master’s degree in organic chemistry at the University of
of Prof. F. Ciardelli and Prof. M. Aglietto (both at the University of Pisa),
Pisa and Scuola Normale Superiore of Pisa (Italy) in 2004 with a thesis
on organosilicon compounds. He completed his Ph.D. in chemistry at and he received his Ph.D. degree in 2000. After a postdoc (2000−2003)
Scuola Normale Superiore of Pisa in 2008, working on transition metal
at the Technical University of Eindhoven (The Netherlands), he joined
nanoparticles. After postdoctoral experiences in heterogeneous catalysis
at Ircelyon and polymer chemistry at the University of Pisa, he moved to the University of Groningen (The Netherlands) firstly as assistant
the University of Groningen in 2011, where he is currently employed as professor and then as associate one. As of November 2013 he is
a postodoctoral fellow in the group of Prof. F. Picchioni and Prof. A. A.
Professor of Chemical Product Technology at the University of
Broekhuis. His present research includes amphiphilic polymers for
industrial applications. Groningen.

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LGA = lactide-co-glycolide
MADIX = macromolecular design via interchange of xanthates
Me6TREN = tris(2-aminoethyl)amine
MOMA = methyl methoxyacrylate
MPC = 2-methacryloyloxyethyl phosphorylcholine
MWD = molecular weight distribution
NaAMPS = sodium 2-acrylamido-2-methylpropane sulfonate
NMP = nitroxide-mediated polymerization
NRET = nonradiative energy transfer
O/W = oil-in-water (emulsion)
P(Q)DMAEMA = poly(quaternized 2-dimethylaminoethyl
methacrylate)
P2VP = poly(2-vinylpyridine)
P4VP = poly(4-vinylpyridine)
Antonius (Ton) A. Broekhuis obtained his Ph.D. degree from the PAA = poly(acrylic acid)
Radboud University in Nijmegen, in 1979. From 1979 to 2003 he held PBA = poly(butyl acrylate)
different research and management appointments in Shell Chemicals in PBD = polybutadiene
Amsterdam, Houston, and London. His work encompassed basic and PBO = poly(butylene oxide)
applied research directed at process and product innovation, as well as at PBzA = poly(benzyl acrylate)
new product development. In 2003 he joined the University of PBzMA = poly(benzyl methacrylate)
Groningen to shape and develop the new chair dedicated to “Chemical PCL = poly(caprolactone)
Product Design and Engineering” (CPD&E) within the chemical PDEAEMA = poly(2-diethylaminoethyl methacrylate)
engineering program. From 2004−2011 he was chairman of the Section PDEGA = poly(diethylene glycol)
of the European Federation of Chemical Engineers on CPD&E. PDI = polydispersity index
PDMA = poly(dimethylacrylamide)
PDMAEMA = poly(2-dimethylaminoethyl methacrylate)
ACKNOWLEDGMENTS PEA = poly(ethyl acrylate)
This work is part of the Research Program of the Dutch Polymer PEB = poly(ethylene-co-butene)
Institute DPI, Eindhoven, The Netherlands, project no. 716. PEGMA/PEOMA/PEOnMA = poly(ethylene glycol meth-
acrylate)
ABBREVIATIONS PEMA = poly(ethyl methacrylate)
ACPA = 4,4′-azobis-4-cyanopentanoic acid PEO/PEG = poly(ethylene oxide)/poly(ethylene glycol)
AIBN = azobisisobutyronitrile PEtSB = poly(diethyldisilacyclobutane)
AM = acrylamide PFMA = 2-(N-methylperfluorobutanesulfonamido)ethyl
ASP = alkaline−surfactant−polymer methacrylate)
ATRP = atom transfer radical polymerization PFOMA = poly(fluoroctyl methacrylate)
bpy = bipyridine PGMA = poly(glycidyl methacrylate)
Ca = capillary number PhIP = poly(hydrogenated isoprene)
CAC = critical aggregation concentration PHMA = poly(n-hexyl methacrylate)
CMC = critical micellar concentration PHOS = poly(4-hydroxystyrene)
CTA = chain tranfer agent PI = polyisoprene
CTAB = hexadecyltrimethylammonium bromide PIB = polyisobutene
CTPPA = 4-cyano-4-thiothiopropylsulfanyl pentanoic acid PIP = polyisoprene
DAMAPS = 3-(N,N-diallyl-N-methylammonium)propane PLA = poly(lactic acid)
sulfonate PMA = poly(methyl acrylate)
DEmMA = dodecyl ethylene glycol methacrylate PMAA = poly(methacrylic acid)
DEPN = N-tert-butyl-N-(1-diethylphosphono-2,2-dimethyl- PMDETA = N,N,N′,N′,N″-pentamethyldiethylenetriamine
propyl) nitroxide PMMA = poly(methyl methacrylate)
DPE = diphenylethylene PnBA = poly(n-butyl acrylate)
DS = degree of substitution PNFHMA = poly(nonafluorohexyl methacrylate)
EGDMA = ethylene glycol dimethacrylate PNIPAM = poly(N-isopropylacrylamide)
EOR = enhanced oil recovery PnOMA = poly(n-octyl methacrylate)
GTP = group transfer polymerization POFPMA = poly(2,2,3,3,4,4,5,5-octafluoropentyl methacry-
H12MDI = bis(4-isocyanatocyclohexyl)methane late)
HDI = hexamethylene diisocyanate PPO/PPG = poly(propylene oxide)/poly(propylene glycol)
HEGMA = methoxy hexaethylene glycol methacrylate PPS = poly(isopropylsulfide)
HEMA = 2-hydroxyethyl methacrylate PS = polystyrene
HLB = hydrophilic−lipophilic balance PSF5 = poly(pentafluorostyrene)
HMPAM = hydrophobically modified polyacrylamide PSGMA = poly(sulfonated glycidyl methacrylate)
HMTETA = 1,1,4,7,10,10-hexamethyltriethylenetetramine PSSNa = poly(sodium stryrene sulfonate)
IFT = interfacial tension PtBA = poly(tert-butyl acrylate)
IPDU = isophorone diurethane PtBMA = poly(tert-butyl methacrylate)
LDA = lithium diisopropylamide PtBOS = poly(4-tert-butoxystyrene)

8550 DOI: 10.1021/cr500129h

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PtBS = poly(tert-butylstyrene)
PTHPMA = poly(tetrahydropyranyl methacrylate)
PTMSMA = poly(trimethylsilyl methacrylate)
PTPFCBPMA = poly(p-(2-(p-tolyloxy)perfluoro-
cyclobutoxy)phenyl methacrylate)
PVA = poly(vinyl alcohol)
PVBC = poly(vinyl benzylchloride)
RAFT = reversible addition-fragmentation chain transfer
polymerization
RITP = reversible iodine transfer polymerization
ROP = ring-opening polymerization
SDS = sodium dodecyl sulfate
SP = surfactant−polymer
TBAB = tetrabutylammonium bromide
TBABB = tetrabutylammonium bibenzoate
TBAOH = tetrabutylammonium hydroxide
tBVBA = tert-butyl vinylbenzoic acid
TEMPO = 2,2,6,6-tetramethylpiperidine-1-oxyl
TFA = trifluoroacetic acid
TMAEMA = 2-trimethylammonioethyl methacrylate
TOA = trioctylamine
TSA = p-toluene sulfonic acid
W/O = water-in-oil (emulsion)
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