View Article Online / Journal Homepage / Table of Contents for this issue

FEATURE ARTICLE www.rsc.org/materials | Journal of Materials Chemistry

Solubilization of polymers by ionic liquids

Neil Winterton
Received 14th July 2006, Accepted 4th September 2006
First published as an Advance Article on the web 2nd October 2006
DOI: 10.1039/b610143g
Published on 02 October 2006. Downloaded by Universidad de Concepcion on 2/1/2023 12:46:10 PM.

Because of the unique characteristics of ionic liquids, novel polymer-containing materials in which
ionic liquids play an important part are currently under intense scrutiny. The ionic liquid may be
used as a medium in which polymerizations take place or into which a polymer may be dissolved
or dispersed to enable a further chemical transformation or materials processing step to be carried
out. Ionic liquid functionality may also be incorporated into the polymer itself, by the use of
suitably derivatized monomers, by a post-polymerization reaction or simply by the formation of a
composite comprising (at least) a polymer and an ionic liquid. The use of ionic liquids in such
chemical and material processing necessitates an appreciation of their effect on reactivity and the
forces that govern solubility and solvation. These topics are at an early stage of investigation,
none more so than in respect of polymers and polymerization. This review surveys published
material up to July 2006 relevant to polymer solubility and solubilization in ionic liquids.

1. Introduction composite comprising (at least) a polymer and an ionic liquid.

The search for new polymeric, composite and hybrid materials
is driven by a range of technological applications and, in turn,
drives efforts to understand intermolecular interactions and
solvation that are fundamental to the control of material
design, processing and final physical form.
Because of the unique characteristics of ionic liquids,1–4
novel polymer-based or polymer-containing materials in which
ionic liquids play an important part are currently under intense
scrutiny. The ionic liquid may be used as a medium in which
polymerizations take place or into which a polymer may be
dissolved or dispersed to enable a further chemical transfor-
mation or materials processing step to be carried out. Ionic
liquid functionality may also be incorporated into the polymer
itself, by the use of suitably derivatized monomers, by a post-
polymerization reaction or simply by the formation of a
Liverpool Centre for Materials and Catalysis, Department of Chemistry,
University of Liverpool, Liverpool, United Kingdom L69 7ZD.
E-mail: n.winterton@liv.ac.uk; Fax: +44 (0)151 794 3583;
Tel: +44 (0)151 794 3585
Some wider aspects of these topics have already been
reviewed.5–8 The intense interest generated so far arises largely
from the nature of the ionic liquids used, usually (but not
invariably9–11) salts derived from combinations of organic
cations and various anions (Table 1 and Fig. 1) with diffuse
charge distributions that ensure that inter-ionic attractions are
relatively weak. A consequence of the latter is that melting
points of ionic liquids are significantly lower than those of
traditional inorganic salts, such as sodium chloride (mp
803 uC), and are often below ambient temperatures.
The use of ionic liquids in chemicals and materials
processing necessitates an appreciation of their effect on
reactivity and the forces that govern solubility and solvation.
Both of these topics, while also of intense current scrutiny, are
at an early stage of development, none more so than in respect
of polymers and polymerization, the subject of this review.
While there is a number of studies that refer, anecdotally and
in passing, to polymer solubility in ionic liquids, very few of
them are focused specifically on this topic, and the latter,
generally, report empirical studies of a somewhat limited
nature.12 Probably the best studied are solutions of cellulose in
chloride ion-containing ionic liquids (see section 3.2.3).

Neil Winterton joined the Table 1 Ionic liquids and abbreviations

Liverpool Centre for
Materials and Catalysis in
1999, after 25 years in
halogenated product R&D with
ICI plc. His prime interests
include seeking to understand
at a fundamental level (and
thereby circumvent) those
physical and chemical charac-
teristics of ionic liquids that
prevent their greater use in
chemicals processing.
Neil Winterton
1,3-Dialkylimidazolium, [rr9im] salts
1,3-Dialkyl-2-methylimidazolium, [2-Me-rr9im]+ salts
1-Alkylpyridinium, [rpy]+ salts
1,1-Dialkylpyrrolidinium, [rr9pyr]+ salts
1,1-Dialkylmorpholimium, [rr9mor]+, salts
1-Alkylpyrazolium, [rpz]+, salts
Tetraalkylammonium salts
Tetraalkylphosphonium salts
r = Methyl (m), ethyl (e), vinyl (v), propyl (p), butyl (b), hexyl (h),
octyl (o), nonyl (n), decyl (d), dodecyl [(dd)]; r9 = methyl (m),
ethyl (e)
With anions: Cl2, Br2, [Cl/AlCl3]2, [CF3SO3]2 abbreviated to
[OTf]2, [4-MeC6H4SO3]2 abbreviated to [OTs]2, [BF4]2, [PF6]2,
[P(OH)2O2]2, [PO4]32, [N(SO2CF3)2]2 abbreviated to [NTf2]2,
[NO3]2, [N(CN)2]2

This journal is ß The Royal Society of Chemistry 2006 J. Mater. Chem., 2006, 16, 4281–4293 | 4281

Published on 02 October 2006. Downloaded by Universidad de Concepcion on 2/1/2023 12:46:10 PM.
Fig. 1 Structures of ionic liquids.
There are several factors to be borne in mind by those who
may be unfamiliar with ionic liquids. Ionic liquids, while being
readily accessible, can, because of the very involatility that
has made them of so much interest, sometimes be difficult to
obtain in an appropriately, and readily verifiable, pure
state.13,14 Impurities that may be difficult to remove from
ionic liquids (and may affect phase behaviour and solvation
phenomena) include materials used in their synthesis and
isolation or to which they may, even adventitiously, be
exposed. In addition, the ubiquitous impurity, water, because
of its low molecular weight, will be present in chemically
significant concentrations even in hydrophobic ionic liquids
(which when fully dried are extremely hygroscopic). Water
may also react with certain fluorinated anions, such as [BF4]2
or [PF6]2,15,16 to form HF. Finally, the use of ionic liquids for
polymer synthesis must address the difficulty of ensuring
complete removal of ionic liquid from the recovered poly-
mer,12,17–19 using analytical methods for estimating retained
ionic liquid of a sensitivity appropriate to the degree of
separation or purification that is required or the level of
contamination that may be acceptable.
This review,20 which attempts to survey published material
up to July 2006, will cover those aspects of the following topics
that have a bearing on polymer solubilization in ionic liquids:
ionic liquids as solvents, particularly for polymers and
polymerizations; polymerization of monomers in ionic liquids;
polymerizable ionic liquids; polymers in ionic liquids and ionic
liquids in polymers; gels and composites; polymer–ionic liquid
interactions.
2. Ionic liquids as solvents
Within the broader context of solvation and solubility, the
cases of polymers as solutes and ionic liquids as solvents are
4282 | J. Mater. Chem., 2006, 16, 4281–4293
View Article Online
often seen as somewhat special cases. On the other hand, while
ionic liquids and polymers indeed have some unique charac-
teristics, their behaviour will still be governed by the same
forces, including dispersion, dipolar, hydrogen-bonding, n–p,
p–p, hydrophobic and ionic, that govern the behaviour of
molecular solvents. Approaches to the measurement of such
forces, and the definition of related solvency scales, have
recently been reviewed by Katritzky et al.21 who identified 184
such scales, based on the use of equilibrium or rate constants
or UV/visible spectroscopy to probe solvation phenomena. It
is clear that a complete appreciation of solvent–solute
interactions must address the bulk properties of solvents, the
inter-molecular (and inter-ionic) interactions between solvents
and solutes, multiphase effects (such as occur in micelles and
plasticization) as well as the consequences of association and
dissociation.
The most widely applied approach uses the multiple
solvatochromic parameters based on linear solvation energy
relationships developed by Taft, Kamlet, Abraham and others.
(See, for instance, ref. 22–24.) Not surprisingly, these (and
related spectroscopic) methods have been applied to ionic
liquids.25–39 However, in some of the earlier reports, the role of
adventitious water was not fully taken into account. Reichardt
has recently reported40 a study of over 30 ionic liquids
encompassing the range of types currently of interest, putting
them onto the ET(30) or EN T scales of polarity, using a
solvatochromic zwitterionic betaine dye. In addition, the
evaluation of ionic liquids as gas–liquid chromatographic
stationary phases,35,41–43 show that they can act both as polar
stationary phases for polar analytes and as non-polar
stationary phases for non-polar analytes, ascribed to the range
and diversity of their solvating characteristics. Solvatochromic
methods, depending on the ionic liquid or the probe
chromophore under consideration, have broadly classified
ionic liquids, in terms of their polarity, with lower alcohols or
dipolar aprotics. The parameters obtained for ionic liquids
reflect a combination of the solute–cation, solute–anion and
solute–ion cluster interactions. While more work will be
needed to resolve these into contributions from individual
anions and cations, recent work, particularly by Welton,44
using correlations of reaction rates in ionic liquids, and by
Davis and co-workers,45,46 using functionalized ionic liquids,
has begun to associate particular aspects of solvation
behaviour with the anion and the cation. Furthermore,
synergism between anions and functionalized cations appears
to contribute to ionic liquid hydrogen-bond basicity.46 The
first estimates of solubility parameters of a polymer (cellulose)
using molecular dynamics appears47 to be of limited use in
predicting the compatibility of cellulose with ionic liquids,
[rmim]X, r = e, b, h;{ X = Cl, CF3CO2.
Efforts48,49 have been made to apply group contribution
methods to ionic liquid–molecular solvent mixtures. While
classical approaches50,51 are unable to deal with long-range
interactions in ionic compounds, more recent quantum
chemical-based thermodynamic prediction models52,53 con-
sider the anion and cation as two separate components of a
{ See Table 1 for a list of representative ionic liquids and the
abbreviations used in this review. Structures are shown in Fig. 1.
This journal is ß The Royal Society of Chemistry 2006

mixture. None of these methods has yet been applied to
polymer-containing systems.
Other experimental approaches, such as the use of dielectric
constant as a measure of solvent polarity, have led to estimates
different from those obtained from the application of LSER
methods. The conventional method for determining dielectric
constants fails because of the high electrical conductivity of
ionic liquids. However, dielectric constants have been mea-
Published on 02 October 2006. Downloaded by Universidad de Concepcion on 2/1/2023 12:46:10 PM.
sured for a series of five [rmim]+ salts, r = e, b, h, using
microwave dielectric spectroscopy,54 e298 falling in the range
8.8–15.2, decreasing with increasing length of r and with the
counter ion, [OTf]2 . [BF4]2 # [PF6]2. These values suggest
that ionic liquid polarity is lower than found by solvatochro-
mic methods and depends markedly on the anion, though the
basis for these conclusions has been contested.55,56 (Related
measurements on [rmim][BF4], r = e, b, using triangular, rather
than sinusoidal, waveform voltage excitation have been
described.57)
Classical approaches to general considerations of solvency
in, and solvation by, ionic liquids, (and, more particularly
where polymers may be the solute58) may be an appropriate
place to begin such an evaluation, though, bearing in mind the
differences between salts and molecular species, we should not
be too surprised if these methods leave something to be
desired. In addition, studies on polymer solubilization in ionic
liquids should be viewed in the much wider context of the
massive literature on polymer–additive interactions59 and
associated polymer–solvent interaction parameters (discussed
in section 3.2.1).
One of the parameters that is used in the solvatochromic
approach of Taft et al. is dH, the Hildebrand solubility para-
meter.60–64 The parameter was initially applied to nonpolar,
non-associated solvents and further refined by Hansen65,66 to
include (independent) dispersion, hydrogen-bonding and
dipolar contributions to these interactions, and later by
Huyskens,67 to take more explicit account of variations in
entropic effects of the solute with solvent molar volume. The
Hildebrand, Hansen and Huyskens approaches are of interest,
both historically and for the purpose of this review, as much of
their work involved polymeric materials and solvent blends
able to dissolve them. These methods employ the cohesive
energy density concept. The cohesive energy, d2H , is the energy
required to produce a mole of cavities in the solvent of size and
shape sufficient to fit molecules of substrate. The energy cost
of creating the cavity is offset by the energy gain resulting from
the interactions between solute and solvent. d2H = [DHvap 2
RT/V], where DHvap is the enthalpy of vaporisation of the
solvent (at 298 K) and V is the molar volume of the solute.
Estimates of DEvap for ionic liquids will be difficult to obtain
as, generally, they have very low vapour pressures. However,
attempts have been made to measure dH for ionic liquids, first
by Swiderski et al.68 using the Kamlet–Taft multiple parameter
approach, from the solvent dependence of the rate constant for
the reaction of singlet oxygen with 1,4-dimethylnaphthalene.
The dH values obtained agree with more recent data,69 for a
series of [rmim]X, r = e, b, h, o, determined by the intrinsic
viscosity method (already widely used to determine dH for
polymers). These dH values were found to depend on the
nature of the anion ([NTf2]2, [OTf]2, [PF6]2) and on the
This journal is ß The Royal Society of Chemistry 2006
View Article Online
Fig. 2 Structures of key polymers.
length of the alkyl group, r. Xu, Cooper and Angell70 have also
commented on the interplay between cohesive energy density
and the characteristics of glasses (such as Tg) derived from
ionic liquids.
It is possible that fresh insights into the interaction of ionic
liquids with polymers (and, indeed, with other substrates)
could arise from the application of the methods of Hansen,
Huyskens and others.
3. Polymers in ionic liquids
Polymerizations are among the earliest chemical transforma-
tions to have been studied in ionic liquids6,7 and now include
most types of homo- and co-polymerizations using a wide
range of monomers. Bearing in mind the very limited number
of studies focused explicitly on the solvency of polymers in
ionic liquids, papers in which such polymerizations in ionic
liquids have been described may incidentally provide such
information. Many of these studies anecdotally report signifi-
cant differences in monomer conversion, polymer molecular
weight, reactivity ratios71 and dispersity when the reaction is
carried out in an ionic liquid rather than a molecular solvent.
Some of these differences can be attributed to interactions
between polymer and medium that are relevant to considera-
tions of polymer solubility. For instance, Noda and Watanabe
report72 that poly(acrylonitrile), poly(AN),{ was insoluble and
poly(2-hydroxyethylmethacrylate), poly(HEMA), was soluble
in [emim]BF4 and [bpy]BF4. Differences (compared with data
from molecular solvents) in the conversion of methyl
methacrylate (MMA), poly(MMA) molecular weights and
molecular weight distributions for 60Co gamma radiation-
induced polymerization in [Me3NCH2CH2OH][ZnCl3] were
ascribed73–76 to a combination of polymer immiscibility and
‘inhomogeneous microdomains’ in the ionic liquid. Strehmel
et al. also note that ionic liquids are able to co-dissolve mono-
mers with widely differing polarities, with their ionic charac-
teristics enabling favourable interactions with highly polar
monomers and the aromatic and alkyl groups present in the
cation interacting favourably with weakly-polar monomers.19
{ See Table 2 for a list of monomers and polymers and the
abbreviations used in this review. Structures of polymers are given in
Fig. 2.
J. Mater. Chem., 2006, 16, 4281–4293 | 4283
 View Article Online

Table 2 Monomers and polymers (and their abbreviations) challenged.82) A similar conclusion was reached by Kaar et al.
in related studies100 on a polytransesterification in the
AN Acrylonitrile
HEMA 2-Hydroxyethyl methacrylate same ionic liquid. Kaar also showed that the transesterification
MMA Methyl methacrylate of MMA proceeds in [bmim][PF6], whereas there is no
St Styrene detectable activity in hydrophilic ionic liquids.100 The out-
Vpy 4-Vinylpyridine
Vpyr 1-Vinyl-2-pyrrolidinone come82 of ring-opening polymerization of caprolactone also
EO Ethylene oxide differed when carried out in [bmim][PF6] (or [bmim]BF4) and
VC Vinyl choride in [bmim][NTf2].
Published on 02 October 2006. Downloaded by Universidad de Concepcion on 2/1/2023 12:46:10 PM.

DMMA N,N-Dimethyl acrylamide

VAc Vinyl acetate
BMA Butyl methacrylate
VDf Vinylidene fluoride
HFP Hexafluoropropene
PDMS Poly(dimethylsiloxane)
PEG Poly(ethylene glycol)
PPG Poly(propylene glycol)
Poly[(veim)Br] Poly(1-vinyl-3-ethylimidazolium
bromide)
Poly[(4-vepy)Br] Poly(1-ethyl-4-vinylpyridinium
bromide)
Poly[(Me3N-CH2CH2MA)Cl] Poly(methacryloyloxyethyl
trimethylammonium chloride)
Other reports conclude that separation of the polymer from
an ionic liquid medium controls the degree of polymeriza-
tion.77–82 For instance, Ma et al.79 show that a well-controlled
reverse atom-transfer polymerization of MMA can be carried
out in [(dd)mim][BF4] but not in [bmim][BF4], and attributed
this to the poor solubility of poly(MMA) in the latter. Other
studies, particularly of free-radical polymerizations,83,84 have
established the critical role ionic liquids play in determining
molecular weights and rates of polymerization by their impact
on rates of propagation and termination, showing that the rate
constants for these processes for MMA in [bmim][PF6]
respectively increase with polarity and decrease with viscosity
as the concentration of ionic liquid increases. A very recent
study85 of BMA polymerization in 29 ionic liquids provided
some evidence linking higher degrees of polymerization with
solvent viscosity, and, further, showing that higher degrees of
polymerisation were obtained in imidazolium- rather than
pyridinium- or ammonium-based ionic liquids.
Other work81,82,86–97 seeks to understand the effect on
polymerizations of changes in the nature of the ionic liquid
that may be relevant to issues of polymer solubility. In
addition, Perrier et al.98,99 have reported that a low molecular
weight material results from the polymerization of styrene (St)
in [rmim][PF6], r = b, h, o, whereas for MMA the greater
solubility of poly(MMA) along this series led to a higher
molecular weight material with low polydispersity. Biedron
et al.90 report that the cationic ring-opening polymerization of
3-ethyl-3-hydroxyoxetane in [bmim][BF4] gives a polyhydroxy
polyether with nearly 100% conversion (though with molecular
weights similar to those obtained in the bulk or in classical
molecular solvents). Intermolecular hydrogen bonding is
reduced, thereby reducing formation of intramolecular aggre-
gates but without affecting intramolecular chain-transfer. The
narrow polydispersity (MW/MN 1.04–1.06) of the polyester
formed from the lipase-catalyzed polycondensation of diethyl
adipate and 1,4-butanediol in [bmim][PF6] was attributed81
to the insolubility of the polymer after it had reached a
certain molecular weight. (This conclusion has recently been
While these and other studies provide hints about the effects
of ionic liquid as solvent, they do not provide even the begin-
ning of a complete picture. For this reason, it is appropriate, in
addition, to mention the importance of studies on ionic liquid
microemulsions and related phenomena,101–113 hybrid redox
polyether melts114–118 and ionic liquid crystals118–124 as these
may give rise to different, and possibly relevant, perspectives
on ionic liquid–polymer solute interactions.
3.1 Ionic liquid polymers
In addition to the preparation and dissolution of discrete
polymeric materials in ionic liquids to form solutions, hybrid
materials comprising characteristics of both polymers and
ionic liquids have been reported. Such polyelectrolytic
materials125 are of considerable interest as components of
composite and functional materials. Interactions between the
ionic domains and the polymer will display similarities to those
exhibited between polymer solutes and ionic liquid solvents.
There is again an extensive literature on this topic and only the
most relevant papers will be reviewed.
It is also important not to lose sight of well known
polymeric materials to which ionic liquids may be similar.
Historical and contemporary studies on long-established
examples, such as ion exchange resins126 and sulfonic acid
membrane materials,127 may provide important insights into
the nature of, and molecular forces acting in, materials similar
to those inspired by recent developments in the studies of
ionic liquids to aid our understanding of polymer solubility
and solubilization.
Solutions of haloaluminate derivatives of poly(4-vinyl-
pyridinium chloride and bromide) were reported by
Watanabe et al.128–130 from the direct reaction of the polymer
with aluminium chloride or by dissolution in 1-alkylpyridi-
nium chloroaluminate melts. Marcilla et al. have adopted a
similar approach131 by dissolving a polymer, poly(1-vinyl-3-
ethylimidazolium X), X = [NTf2], [BF4], Br, in the correspond-
ing ionic liquid, [bmim]X, providing homogeneous mixtures
showing no phase separation over periods of weeks. Halide
exchange of polycations with anions that typically yield
hydrophobic ionic liquids, such as [NTf2]2, produce materials
that are recognisable to those working in ionic liquids.
Examples have been described by Marcilla et al.132,133 who
have treated a series of polycations, poly(1-vinyl-3-ethyl-
imidazolium bromide), (1), poly(1-ethyl-4-vinylpyridinium
bromide) (2), and poly(methacryloyloxyethyltrimethylammo-
nium chloride) (3), with seven counter-anions such as [PF6]2,
[OTf]2, [NTf2]2, [(CF3CF2SO2)2]N]2, dodecylbenzenesulfo-
nate, [OTs]2, and bis(2-ethylhexyl) hydrogen phosphate.
The polymeric ionic liquids show a range of solubility
behaviour, including that with ionic liquids, that depends on

4284 | J. Mater. Chem., 2006, 16, 4281–4293 This journal is ß The Royal Society of Chemistry 2006

the counter-anion. Ogata et al.130 reported the dissolution into
[NMe3Et][AlCl4] of a series of polycations, [eg, 4] prepared
by reacting bis(N-heterocycles) with a,v-dihaloalkanes.
Stimulated by the need for ionic polymer electrolytes for
quasi-solid-state dye sensitized solar cells,134 Suzuki et al.,135
using the same approach, have prepared an imidazolium
polymer in which the polymer chains, consisting of alkyl-
midazolium salt units, are formed by reacting alkyl-bis(imida-
Published on 02 October 2006. Downloaded by Universidad de Concepcion on 2/1/2023 12:46:10 PM.
zole)s and diiodoalkyls.
Mainly driven by the need to develop polymer electrolytes
that combine compositional stability (through the avoidance
of evaporation of liquid components), high (and selective)
ionic conductivity and low glass transition temperature, many
workers have investigated the preparation, characterization
and application of polymers derived from polymerizable
monomeric ionic liquids. These studies have used materials
in which the polymerizable unit could be found in the anion,
the cation or both. A detailed discussion of this topic lies
beyond the scope of this review.
3.2 Polymer solubilization in ionic liquids
A straightforward means of obtaining a polymer–ionic liquid
composite would be the simple dissolution of a polymer in an
ionic liquid. There are surprisingly few studies that have
undertaken even an empirical study of this process.
3.2.1 General issues. Strictly speaking, solubility of one
compound in another is determined by thermodynamic
factors. General experience, using classical solvents, is that
dissolution is relatively rapid and, even if several hours are
required to obtain an equilibrium condition, this rarely
presents any practical difficulty. However, dissolution of
polymers may present some problems, compounded if we are
attempting to dissolve a polymer into an ionic liquid at
temperatures at which the viscosity of the latter is high enough
to represent a serious barrier to mass and phase transfer.
Studies of polymer solution behaviour136 led Flory137 and
Huggins138 to propose a model of the thermodynamics of
polymer solutions, which addresses the difference in molecular
sizes of polymeric chains and molecular solvents, particularly
in estimating the entropy of mixing. The Flory–Huggins
theory introduces a parameter, x, to account for the energy of
intermixing of solvent and polymer. While polymer–solvent
interaction parameters64,139 have been extensively studied,
there are no reports of the application of the Flory–Huggins
theory to solutions of polymers in ionic liquids.§ Some of the
methods for determining such parameters may be confounded
by characteristics of ionic liquids, such as the absence of
measurable vapour pressure. However, studies of polymer
solutions in mixed solvents140 and in salt solutions,141 and
solutions of polyelectrolytes,142 may provide a starting
point for contemplating such investigations. It has been
recognised140b that a description of the phase behaviour of
ternary systems, such as those containing a polymer and two
solvents, requires x for the corresponding binary systems to be
§ Flory–Huggins-type approaches applied to ionic liquid mixtures with
non-polymer solutes have been described. See ref. 230 and earlier
papers by Rebelo and co-workers cited therein.
This journal is ß The Royal Society of Chemistry 2006
View Article Online
independently measured. Considering an ionic liquid–polymer
solution has such a ternary system may represent just one
initial approach.
Dissolution of a polymer may require initial dissolution of
the solvent in the polymer itself, leading to swelling or
plasticization (see section 4.1) that might facilitate combina-
tion of polymer and solvent into a single phase. Because mass
transfer is a kinetic phenomenon, an appreciation of the rates
of these processes and, thus, the time necessary for equilibra-
tion between excess solid and solution, are both required. This
information is not generally available. Similarly, when a
polymer has been synthesized in an ionic liquid, should the
failure to observe phase separation of the polymer be seen as a
guide to thermodynamic solubility or an indication that
insufficient time has elapsed for phase separation to occur?
In a number of reported instances, this is quite clear and the
polymer quickly separates. In others, where changes in key
mixture properties (such as viscosity) with degree of poly-
merization may control phase separation, evidence suggests
that such separation can take weeks to become apparent. A
recent report113 notes that the initial micelle structures formed
on dissolution of poly((1,2-butadiene)-b-ethylene oxide)
diblock polymers in [bmim][PF6], remain unchanged over
time. Similarly, where a volatile molecular solvent has been
used to bring polymer and ionic liquid into a single solution
phase, evaporation of the volatile component may well yield a
mixture that may take several weeks to reach equilibrium
(and which may involve segregation of a solid polymer phase).
These factors represent a significant challenge as the expected
working lives of devices9 that employ ionic liquid–polymer
composites could well be governed by some of these longer
term effects.
3.2.2 Solubilization. Reports describing the solubility of
polymers in ionic liquids are limited. Probably the first are
those of Watanabe et al. who describe the insolubility of
poly(MMA), poly(St), poly(AN) and poly(EO) in the [bpy]Br–
AlCl3 ionic liquid (though the precise composition of the melt
was not given).129,130,143 Wilkes144 investigated extraction of
pre-formed polymers, including nylon 6, high- and low-density
polyethylene, poly(VC), poly(St), black rubber, and butyl
rubber, by basic, acidic and super-acidic [emim]Cl/AlCl3.
Forsyth et al.145 were able to dissolve poly(N,N-dimethyl
acrylamide), poly(DMMA), poly(AN), poly(1-vinylpyrrolidi-
none), (5), and poly(VPyr-co-VAc) in [Me3NBu][NTf2]. Noda
et al.72 report the solubility of poly(HEMA) and insolubility of
poly(MMA) and poly(AN) in [bpy][BF4] and the insolubility
of poly(AN) and the solubility of poly(HEMA) in
[emim][BF4]. Benton and Brazel, in a later study17 of the
polymerization St, MMA and HEMA in ionic liquids, carried
out qualitative tests of the solubility of poly(St), poly(MMA)
and poly(HEMA) in [bmim][PF6] (respectively, insoluble,
insoluble, insoluble) or [bmim]Cl (insoluble, insoluble,
soluble). (Significantly, it was reported that poly(HEMA)
retained [bmim]Cl on segregation, sufficient to degrade its
properties, though solvent treatment led to a diminution of the
impact of this contamination.) The order of miscibility of
polymers with [Me3NCH2CH2OH][ZnCl3] is poly(MMA) .
poly(BMA) . poly(St).146 High molecular weight atactic
J. Mater. Chem., 2006, 16, 4281–4293 | 4285
 View Article Online

poly(AN) may be formed10 from AN in KSCN/NaSCN
eutectics. Poly(AN) was shown to be soluble in both the
eutectic and in the molten hydrate, (LiClO4.3H2O) and
recoverable on cooling the melt. Further studies of polymer
electrolytes generated by the dissolution of poly(AN), poly-
(vinylidene fluoride) poly(VdF), poly(vinylidene fluoride-co-
hexafluoropropene) poly(VdF-HFP), poly(VAc) and poly(EO)
in [emim]3PO4 have been reported by Lewandowski.147,148
Published on 02 October 2006. Downloaded by Universidad de Concepcion on 2/1/2023 12:46:10 PM.
[bmim][PF6] and [omim][NTf2], chosen to be representative of
a range of typical anions and cations). As trial experiments
with powdered samples showed, the majority of polymers were
apparently insoluble in both [bmim][PF6] and [omim][NTf2]
(5 wt% concentration). Solutions were, thus, prepared by
co-dissolution using volatile molecular solvents, followed
by evaporation under vacuum. Possible phase separation was
monitored, qualitatively, by the onset of turbidity and

Ternary systems poly(AN)–ionic liquid–sulfolane have also
been described, where the ionic liquids are [emim][BF4],
[bmim][PF6] and [bmpyr][NTf2]. More recently, in a study
of cellulose-polymer blends, the solubility of poly(VAc),
poly(HEMA), poly(AN), poly(VC), poly(ethylene glycol),
poly(propylene glycol), DNA and other materials in
[bmim]Cl is investigated.149
A later, more comprehensive, though still empirical, study
was undertaken by Snedden et al.12 This group prepared a
series of polymer solutions (from homopolymers of acrylic
acid, BMA, EO, St, VPy, VPyr and copolymers of 1-vinyl-
imidazole and 1-vinyl-2-pyrrolidinone and 4-vinylimidazolium
homopolymer) in three different ionic liquids ([emim][BF4],
precipitation over a period of eleven to fifteen weeks. The
results are presented in Table 3. Significantly, even after this
period, it was impossible to say that no further change would
occur. [omim][NTf2] appeared to be the most effective solvent
for a wide range of polymers. The behaviour of [emim][BF4]
was similar to that of [bmim][PF6]. Polymers that showed
good initial solubility in all three ionic liquids included the
1-butylpyridinium polyelectrolyte, poly[(4-vinyl-1-butyl-
pyridinium)Br-co-4-vinylpyridine], and the hydrophilic poly-
ether, poly(EG). Highly hydrophobic poly(St) was insoluble in
all three ionic liquids. On the other hand, the relatively
hydrophobic poly(BMA) was freely soluble in two of the ionic
liquids and completely insoluble in the third, for reasons that

Table 3 Phase behaviour or selected polymer solutions in ionic liquids. (Reprinted from ref. 12. Copyright 2003, American Chemical Society)
Ionic liquidb
[emim][BF4] [bmim][PF6] [omim][NTf2]
Polymera Weeks 0 2 4 6 11 0 2 4 6 11 0 2 4 6 15

A P(BuVPBr–VPy) + + + + + + + + + + + + + + +
B P(BuVPBr–VPy–styrene) o 2 2 2 2 o o 2 2 2 + + c c c
C P(BuVPBr–VPy–BMA) 2 2 2 2 2 o 2 2 2 2 c c c c c
D P(BuVPTf2N–Vpy) + + + + + c c c c 2 + + + + +
E P(MeVIm[NTf2]) 2 2 2 2 2 c c c c c + + + + +
F P(VIm–VPyr), 50% VPyr o 2 2 2 2 + c o o 2 + + + + +
G P(MeVImMeOSO3–VIm–VPyr) + + + + + + + c c c + + + + +
H P(MeVImCl–Vim–VPyr) + + + + + c c c c c + + o o 2
I P(MeVImMeOSO3–Vim–VPyr–VCap) o o o o o + c c c c + + + + +
J P(acrylic acid), Mw 2 6 103 g mol21 + + + + + 2 2 2 2 2 2 2 2 2 2
K P(BMA), Mw 337 6 103 g mol21 + + + + + 2 2 2 2 2 + + + + +
L P(EG), Mw 10 6 103 g mol21 + 2 2 2 2 + + + + + + + + + +
M P(St), Mw 30 6 103 g mol21 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2
N P(VPy), Mw 160 6 103 g mol21 2 2 2 2 2 2 2 2 2 2 + c 2 2 2
O P(Vpy–St), 10% styrene 2 2 2 2 2 2 2 2 2 2 + c 2 2 2
P P(VPy–BMA), 10% BMA 2 2 2 2 2 2 2 2 2 2 + c 2 2 2
Q P(Vpyr), Mw 10 6 103 g mol21 + + + + 2 + + c 2 2 + + + + 2
a
A–E synthesized, F–Q commercially available; abbreviations: BMA (butyl methacrylate), [NTf2]2 [(CF3SO2)2N2], VCap (1-vinylcaprolactam),
VIm (1-vinylimidazole), VPy (4-vinylpyridine), VPyr (1-vinyl-2-pyrrolidinone). Mw values for A–I, O and P were not determined.
Materials: poly(1-vinylimidazole-co-1-vinyl-2-pyrrolidinone) F (Luvitec VPI K72W; comonomer content = 50%) was kindly donated by BASF.
Poly(1-methyl-3-vinylimidazolium methylsulfate-co-1-vinylimidazole-co-1-vinyl-2-pyrrolidinone) G (Luviquat MS370), poly(1-methyl-3-
vinylimidazolium chloride-co-1-vinylimidazole-co-1-vinyl-2-pyrrolidinone) H (Luviquat HM552) and poly(1-methyl-3-vinylimidazolium
methylsulfate-co-1-vinylimidazole-co-1-vinyl-2-pyrrolidinone-co-N-vinylcaprolactam) I (Luviquat HOLD) were obtained from Fluka.
Poly(acrylic acid) J (Mw = 2000 g mol21), poly(BMA) K (Mw = 337 000 g mol21), poly(EG) L (Mw = 10 000 g mol21), poly(VPy) N (Mw =
160 000 g mol21), poly(VPy-co-St) O (styrene content = 10%), poly(VPy-co-BMA) P (BMA content = 10%) and poly(VPyr) Q (Mw =
10 000 g mol21) were obtained from Aldrich. Poly(St) M (Mw = 30 000 g mol21) was obtained from Polysciences. Polymers A–C were
prepared by the respective quaternization reaction of polymers N–P with butyl bromide in chloroform. Polymer D was prepared by the ion
exchange reaction of aqueous solutions of polymer A and Li[NTf2]. Polymer E was prepared by the persulfate-initiated free-radical
polymerization of [veim][NTf2]. Divinylbenzene (DVB; tech., 55%, mixture of isomers), trimethylolpropane trimethacrylate (TRIM; tech.),
4-vinylpyridine (VP; 95%) and 1-vinyl-2-pyrrolidinone (VPyr; 99%) were obtained from Aldrich and used as supplied. a,a9-Azoisobutyronitrile
(AIBN) was purchased from Fisher and recrystallized (methanol) prior to use. [bmim][PF6] (¢99%) and [emim][BF4] (¢98%) were obtained
from Solvent Innovation. [omim][NTf2] was prepared by the ion exchange reaction of aqueous solutions of [omim]Cl and Li[NTf2] according
to a literature method.229 b Procedure for polymer solubility screening, Polymers A–Q (25 mg) were individually dissolved in solvent (0.5 ml:
acetone D, E; MeOH A–C, F–J; CH2Cl2 K–Q) and the resultant polymer solutions (5 wt%) injected (glass syringe) into glass vials (2 ml
capacity, fitted with silicone–PTFE seals) containing ionic liquid (0.5 ml; [emim][BF4], [bmim][PF6] or [omim][NTf2]) and the resultant solutions
briefly agitated. A syringe needle was inserted into each sample vial lid seal (to provide an air bleed) and the volatiles removed in vacuo (oil
pump) at 50 uC for 3 d. Phase changes in the ionic liquid–polymer solutions were monitored over the course of 11 ([emim][BF4], [omim][NTf2])
or 15 ([bmim][PF6]) weeks. Key: + (clear solution), c (cloudy), o (opaque), 2 (precipitate).

4286 | J. Mater. Chem., 2006, 16, 4281–4293 This journal is ß The Royal Society of Chemistry 2006

are not immediately obvious. Several of the polymer solutions
exhibited slow phase separation, suggesting that both polymer
dissolution and phase separation may be mass- or phase-
transfer limited. Many initially homogeneous polymer–ionic
liquid solutions exhibited phase separation over periods of
days to weeks. These experiments revealed unexpectedly varied
behaviour, indicating that the factors responsible for polymer
solubility in ionic liquids are complex and not readily
Published on 02 October 2006. Downloaded by Universidad de Concepcion on 2/1/2023 12:46:10 PM.
predicted. The detailed phase behaviour of polymer–ionic
liquid mixtures thus requires more in-depth investigation.
Observations made by Marcilla et al.133 suggest that care
should be taken in applying the principle that ‘like dissolves
like’ too literally. It might have been expected that the
polymerized ionic liquids, poly(1-vinyl-3-ethylimidazolium
X), poly([veim]X], would be soluble in the ionic liquid [veim]
[NTf2]. When X = [OTf]2, [NTf2]2 and [N(SO2CF2CF3)2]2
they were, but when X = Br2, [BF4]2, [PF6]2 they were not.
Recently, the formation of a stable stereo-complex
between stereo-regular isotactic poly(methyl methacrylate)
(it-poly(MMA); mm = 97%) and syndiotactic poly(methyl
methacrylate) (st-poly(MMA); rr = 90%) has been demon-
strated150 in [bmim][PF6], a phenomenon which is associated
with thermoreversible gel formation. The tendency to complex
formation was particularly sensitive to the choice of ionic
liquid counter-anion, being slower in [bmim][NTf2] and not
apparent at all in [bmim][OTf]. Both it- and st-poly(MMA)
were insoluble in [bmim][BF4].
3.2.3 Related systems. The situation is potentially further
complicated by the occurrence of phenomena such as
microsolvation, microsegregation, plasticization and gel for-
mation, that may provide a thermodynamic well into which
the system can (eventually) fall.151 Microphase separation has
been proposed, from the observation, using differential
scanning calorimetry, of two Tgs152 for a poly(acrylonitrile-
co-butadiene) rubber in [emim][NTf2]. Also, unexpected
phenomena may arise, such as the interesting formation of
gels between ionic liquids and carbon nanotubes (‘‘buck-
ygels’’). Fukushima et al.153,154 have investigated the rheolo-
gical properties of these materials and suggest that they are
formed by physical cross-linking of the nanotube bundles,
mediated by local molecular ordering of the ionic liquids,
rather than by entanglement of the nanotubes. The physical
gelation of ionic liquids by the addition of low molecular
weight organic gelators has also been described155 for a series
of twenty four typical ionic liquids, combining six anions with
six cations. Spectroscopic studies suggest that intermolecular
hydrogen bonding between amido groups was responsible
for gelation. Kimizuka and Nakashima156 have employed
ether-containing ‘‘sugar-philic’’ ionic liquids, [rmim]Cl, r =
MeOCH2, MeOCH2CH2, to dissolve a series of carbohydrates.
Solutions of amide-group enriched glycolipids give ionogels
that self-assemble to give bilayer membranes or fibrous
aggregates. Sawada et al. have found157 that a 2-acrylamido-
2-methylpropanesulfonic acid oligomer (6), endcapped with
fluoroalkyl groups, such as –CF(CF3)OC6F13, forms a highly
proton-conducting gel with 1-methylpyrazolium tetrafluoro-
borate, [mpz][BF4], under non-crosslinked conditions. Cross-
linked poly(ethylene glycol) networks for gelation of ionic
This journal is ß The Royal Society of Chemistry 2006
View Article Online
liquids have also been synthesized.158 Short- and intermediate-
range order is revealed159 from molecular dynamics
simulations of [rmim]+ and poly(EO). Hydrogen-bonding
interactions, similar to those thought to be responsible for
dissolution of cellulose and related materials in chloride-based
ionic liquids, have been invoked160 to explain dissolution in,
and gelation by, [rmim]Cl, r = e, b, h, o, d, and [bmim]Br of
polyrotaxanes consisting of a-cyclodextrin and PEG. Other
polymer-gelled systems are discussed in section 4.2.
A consideration of solubilization of synthetic polymers in
ionic liquids cannot properly ignore related work concerned
with natural or semi-synthetic polymers, such as DNA,
proteins and polypeptides, polysaccharides, sugars, glycoli-
pids, silk, keratin and kerogen. Only strictly relevant work is
discussed here.
Synthetic polymers produced in ionic liquids in enzyme-
catalyzed reactions have already been mentioned in section 3.
None of the studies of such transformations report control
experiments in which the solubility of native, or synthetic,
polypeptides was examined. Dipeptide formation was first
reported161 using an enzyme-catalyzed process in [bmim][PF6].
Non-enzymatic oligopeptide formation (also in [bmim][PF6]
or similar ionic liquids) results97 from treatment of solid
amino acids at .100 uC or by coupling reactions involving
N-protected amino acids and aminoesters.162,163
While an early study reports the ability of chloroaluminate-
based ionic liquids to dissolve the usually highly intractable
material, kerogen,164 and draws attention to the unique ability
of this class of solvents, it is later work on cellulose and DNA
that has generated the greatest interest. Ohno first reported the
interactions of DNA with ionic liquids, describing a series of
conducting flexible films containing up to 94% (by weight)
[emim][BF4].165 Two Tgs are seen for this film, ascribed
to microphase separation. (See also ref. 166 and 167.)
Neutralization of DNA with fluoroboric acid, in an attempt
to produce the expected168 ionic liquid domains, gave only a
poorly conducting powder showing a low ionic conductivity.
However, addition of [emim][BF4] produced a highly conduct-
ing film. Very recently, a material with ionic liquid domains
also resulted169 from the exchange of the counter-cation of the
phosphate groups of double-stranded DNA by a series of
imidazolium cations, using [rmim][P(OBu)2O2], r = e, b, o and
(dd), as models. These ion exchanged materials were also
poorly conducting, but addition of [emim][BF4] significantly
raised conductivity because of the formation of a continuous
ionic liquid domain.166
Swatloski et al. note170 that the first suggestion that cellulose
should be soluble in a molten salt, [epy]Cl (MPt 118 uC), was
made in a US patent171 as long ago as 1934. Cellulose was
found106,172,173 to dissolve well in [bmim]Cl, the rate of
dissolution aided by the application of microwave heating,
and in the inorganic molten salts, LiClO4?3H2O, NaSCN–
KSCN–LiSCN?2H2O and LiCl–ZnCl2–H2O.11,174 Fisher
et al.11,174 categorise behaviour (as a pointer to the nature of
the molten salt–cellulose interaction) into four types: simple
dissolution; swelling; decomposition; no effect. The favorable
solution of cellulose in [bmim]Cl and related solvents appears
to be driven by hydrogen-bonding effects,148 characterized by
a very high hydrogen-bond basicity coefficient175 in the general
J. Mater. Chem., 2006, 16, 4281–4293 | 4287

form of the linear solvation energy equation22 for the ionic
liquid. More recently,176 NMR relaxation studies suggest a
1 : 1 stoichiometry for the association between chloride and
carbohydrate hydroxyl groups. These observations are stimu-
lating the use of ionic liquids, such as [rmim]X, r = e, b; X =
Cl, Br, [N(CN)2], in the processing of cellulose and related
materials177,178 and the protection179 and licensing180 of
associated intellectual property.
Published on 02 October 2006. Downloaded by Universidad de Concepcion on 2/1/2023 12:46:10 PM.
While proteins are usually insoluble in ionic liquids156
(though may be dispersed in them), some (for instance,
monellin181) may have limited solubility. More recently,
Fujita et al.182 have reported that [bmpyr]- and [Me3NCH2-
CH2OH]-based ionic liquids with [N(CN)2]2 [P(OH)2O2]2 or
saccharinate counter-anions can dissolve cytochrome c with
retention of its secondary structure, even at elevated tem-
peratures. Protein solubilization can also be achieved by
functionalization of either the protein or the ionic liquid with
polyether chains.183 For instance, for cytochrome C to be
made readily soluble in [bmim][NTf2], poly(EO) residues,
sufficient to comprise 60% mole fraction of the functionalised
material, needed to be introduced at amino residues of the
protein.
While the activity and stability of enzymes in ionic liquids
have been associated with their polarity, hydrogen-bond
basicity and anion nucleophilicity, the stability of protease
in aqueous solutions containing ionic liquids has been
discussed184 in terms of the kosmotropic and chaotropic
character of the anion and cation.
3.2.4 Polymer–ionic liquid interactions in solution. The nature
of solute–ionic liquid interactions is an important focus of
attention that depends crucially on an understanding of the
liquid structure of ionic liquids185 as well as the energetics
and dynamics of various inter-ionic processes. Of particular
interest are those studies, (of small but increasing number) that
have addressed polymer–medium interactions directly, using a
range of physical and spectroscopic (and computational159)
techniques, including 13C and 35/37Cl NMR, pulsed-field-
gradient spin-echo NMR, atomic force microscopy (AFM),
small angle neutron- (SANS) and X-ray scattering (SAXS),
dynamic light scattering (DLS), time-dependent fluorescence,
FT-Raman spectroscopy and cryo-transmission electron
microscopy (TEM).
Dynamic atomic force microscopy (AFM) has been used by
Habrard et al.9 to study the phase microseparation occurring
in blends of molten salts ([NHex4][NTf2], [NOct4][NTf2],
[PHex3C12H25][NTf2]) and a group of fluorine-based lumi-
nescent conjugated polymers to investigate premature
electrical aging of organic electroluminescence devices. The
molten salt forms self-organized microdomains, whose size
and density depend on the polymer side chains and molecular
weight and on the nature of the ionic liquid. Aging is
attributed to the degradation of the interface between the
polymer and salt domains.
Stancik et al.186 have characterized the assembly of a series
of poly(St)–imidazolium-functionalized poly(St)–(IL) block
copolymers using SANS and DLS to determine the micelle
size and shape in dilute solutions and to assess micellar
interactions in concentrated solutions. The length of the IL
4288 | J. Mater. Chem., 2006, 16, 4281–4293
View Article Online
block is found to determine the micelle dimensions. The
micelles can sequester water. Firestone et al.,119,120 using
SAXS, have noted hydrogen-bonding interactions between
anion and water in ionogels formed from [dmim]X, X = Br,
[NO3], and water.
13
C-NMR spectroscopic studies of the chemical interaction
between salt and polymer in poly(AN) in eutectic (NaSCN–
KSCN) or molten hydrate (LiClO4?3H2O)10 show that the
dissolution of the polymer in KSCN–NaSCN (at 140 uC) is
accompanied by splitting of hydrogen bonds between a-H and
CN on the polymer. 13C NMR studies on [bmim]Cl solutions
of cellulose and related oligomers have been reported by
Moulthrop et al.187 and on cellulose solutions in [bmim]Cl,
[3-Me-bpy]Cl and [Me2N(CH2Ph)(C14H29)]Cl.188 The latter
study showed that no depolymerization of the polysaccharide
occurred in the ammonium or imidazolium salt, but extensive
degradation occurred in the pyridinium salt. The reasons for
this behaviour are not understood. Polymer–ionic liquid
interactions were also invoked189,190 to account for the
qualitatively different rheological behaviour of poly(1,3-
phenyleneisophthalimide) dissolved in [bmim]Cl or in
dimethylacetamide/lithium choride189 and poly(arylsulfone)
dissolved in [bmim]Cl or in dimethylacetamide.190 Pulsed-
field-gradient spin-echo NMR has been used to deter-
mine191,192 the diffusion coefficients of cation and anion in
[2-Me-bmim][NTf2] and poly(VdF-HFP) polymer gels. The
transference number of the ionic liquid and the polymer gel has
been calculated. The conductivities of both the ionic liquid and
polymer gel have been measured as a function of temperature
and the activation energies calculated. Related investigations
have been undertaken in systems based on chloroaluminate
ionic liquids. Using confocal Raman spectroscopy, Schafer
et al.193 show that, in composites of [bmim]X, X = [BF4], [PF6],
[NO3], [NTf2] and a sulfonated poly(tetrafluoroethylene)
membrane, Nafion1, and a non-charged PDMS membrane,
the ionic liquids are better seen as behaving like electrolytes
rather than solvents (with [bmim]+ engaging in ion exchange
with the counter cation of the Nafion1). Interestingly, while
addition of the miscible poly(VPyr) to the ionic plastic crystal
[pmpyr][PF6] significantly increases194 mechanical strength and
decreases conductivity, it has little effect on phase behaviour.
In one of the few studies of its type, time resolved- and
steady state fluorescence of poly(dimethylsiloxane), end-
labelled with pyrene units, in [bmim][NTf2] (with up to 50%
toluene) shows the pyrene end-groups are located in a PDMS-
rich micro-environment.195
4. Polymer–ionic liquid composites
One of the main factors motivating the study of polymer–ionic
liquid interactions is their bearing on the properties of
technically important composites, particularly for solid elec-
trolytes for use in battery and fuel cell applications. Because of
a combination of involatility, thermal and electrochemical
stability and high conductivity, ionic liquids (particularly the
more water-stable non-haloaluminate salts) are seen as having
the potential to play an important role in the development of
such materials with optimal properties. Whether these
composites represent true homogeneous solutions (that is, at
This journal is ß The Royal Society of Chemistry 2006

thermodynamic equilibrium), or are better seen as blends
or mixtures with discrete, but possibly metastable,
domains and interfaces, leaves many unanswered questions
relevant to a more fundamental understanding of the under-
lying phenomena.
4.1 Plasticization
Published on 02 October 2006. Downloaded by Universidad de Concepcion on 2/1/2023 12:46:10 PM.
Processing of many industrial important polymers for
materials applications relies on the addition of plasticizers.59
Plasticizers act by lowering the glass transition temperature,
Tg, and aid flexibility. The molecular-level interactions
between polymers and additives responsible for this techno-
logically very important effect will closely resemble those
associated with solvation and are clearly relevant to this
review.
While there are several reports describing composites
containing ionic liquid in which plasticization is thought to
occur or which highlight the role of ionic liquids in polymer
plasticization, there is little yet known of the relationship
between ionic liquid composition or structure and the
plasticization effect. The summary will thus be brief.
Watanabe128 first described the interaction between an ionic
liquid, [rpy]Cl/AlCl3, and a polymer poly(4-vinyl-1-butyl-
pyridinium) chloride) in terms of a plasticization effect. The
purposeful use of imidazolium ionic liquids, [bmim][PF6],
[hmim][PF6], for the plasticization of poly(MMA) was first
addressed by Scott et al.196–198 The two ionic liquids were
compared with an industry standard, dioctyl phthalate. A
linear relationship between Tg and ionic liquid content was
seen, up to 50 wt%. This work has recently been extended to
poly(VC),199 evaluating, in addition, phosphonium salts with
Cl2, [NTf2]2 and decanoate counter ions. Lewandowski et al.
also identify [emim][BF4], [bmim][NTf2] and [bmim][PF6]
as acting as polymer plasticizers.200 On the other hand,
[bmim]BF4 is reported to be a hardener for an epoxy resin.201
4.2 Composites
The properties of composites will be governed by the same
inter-molecular and inter-ionic interactions that control
solubility. However, the delineation and understanding of
these interactions is constrained by both compositional and
morphological complexity and questions concerning whether
or not the system is at thermodynamic equilibrium. Many
studies have been published on these and related composite
materials,202 assessing characteristics (ion transport, mechani-
cal, thermochemical, electrochemical) relevant to a specific
application, but which are often interpreted in terms of
polymer–medium interactions that may be relevant to this
review.151,203 Some selected work is thus highlighted. Those
reports that have addressed polymer–medium interactions
directly have already been summarised in section 3.2.4.
Many of these materials are made by mixing the compo-
nents together (sometimes with a third material acting as a
co-solvent which may subsequently be removed) to form gelled
systems. In a small number of cases discussed in this section
in situ polymerization is carried out. Early studies by Carlin,
Fuller et al.204,205 led to the first ionic liquid gel electrolytes
from [emim]X, X = [OTf], [BF4] and poly(VdF-HFP). In
This journal is ß The Royal Society of Chemistry 2006
View Article Online
another early study, Forsyth et al.145 prepared polymer-in-salt
electrolytes, obtained by mixing poly(DMMA), poly(AN),
poly(VPyr), and poly(VPyr-co-VAc) in [Me3NBu][NTf2],
showing that the addition of high Tg polymers led to decreased
conductivity. Tiyapiboonchaiya et al.206,207 have explored
similar materials, particularly poly-(vinylpyrrolidone-co-vinyl
acetate), P(VP-co-VAc), in [emim][NTf2] and poly(DMAA) in
[Me3NBu][NTf2] producing ion-conducting liquids and gels.
The same group has also made polyelectrolyte-in-ionic liquid
composites from a combination of a lithium 2-acrylamido-2-
methyl-1-propanesulfonate and DMMA with [emim][N(CN)2],
which acts as a good solvating medium for the polyelectrolyte.
Gelled materials have been described by Sutto et al.208–210
from poly(VdF-HFP), or from a combination of poly(VdF-
HFP) and poly(acrylic acid), with ionic liquids [emim][BF4],
[2-Me-pmim]X, X = [BF4], [NTf2], [2-Me-bmim]X, X = [BF4],
[PF6], [NTf2], by Yeon et al.211 from poly(VdF-HFP) and
[rmim]X, (r = HOCH2CH2; X = [BF4], [PF6]) and by Singh
and Sekhon212,213 from poly(VdF-HFP) (and a series of other
polymers, poly(EO), poly(MMA), poly(MA), poly(AN) and
poly(VdF)) and [2-Me-omim]X, X = [BF4], [PF6], [OTf],
[NTf2]. Bansal et al.214 suggest that the temperature depen-
dence of the conductivity and transport properties of
poly(VdF)–mixed organic carbonates (as plasticizers)–
Li[N(SO2C2F5)2], a similar composition with 5% (by weight)
[emim][N(SO2C2F5)2] and poly(VdF)-Li[N(SO2C2F5)2]–62.5%
[emim][N(SO2C2F5)2] are consistent with the free volume
model of ion transport. A similar investigation215 of ionic
conductivities of mixed poly(VdF–HFP)–solvent (propylene
carbonate)–ionic liquid ([bmmor][NTf2]) has been reported.
High temperature proton-conducting membranes based on
perfluorinated ionomer membrane–ionic liquid composites
have also been described,216,217 prepared by imbibing the ionic
liquid into the polymer, though uptake was usually ,30%.
Using a molecular swelling solvent to aid the process, up to
440% of imidazolium bis(trifluoromethanesulfonyl)amide,
[Him][NTf2], has been incorporated into non-fluorinated
polymers based on rigid sulfonated aromatic backbones
crosslinked with diamine-terminated PEO oligomers.218
Perfluorosulfonic acid membranes and polytetrafluoroethylene
filter membranes have been used219 as polymer matrices with
[emim]X, X = [NTf2], [OTf], [BF4]. It was suggested that
interactions between the matrix and ionic liquid enhance the
thermal stability of the composites.
Solid polymer electrolytes based on ionic liquid–polymer
composites fall into two main categories:220 salt-in-polymer
and polymer-in-salt electrolytes. (Studies of such systems not
involving ionic liquids (see, for instance, ref. 202, 221, 222)
have a clear bearing on polymer–ionic liquid interactions, but
are beyond the scope of this review.) Both categories represent
attempts to enhance ionic conductivity of the matrix. Much
early work was done using polyethers, where addition of salt
resulted in increases in Tg (arising from lithium ion–ether
dipole interactions or lithium ion–poly(ether) coordinative
cross-linking223) an unacceptable outcome that can be
circumvented only at very high salt concentrations.203 In
addition, the ionic conductivity is often dominated by the
anion and several strategies have been adopted to resolve this.
By functionalising the termini of ethylene oxide oligomers with
J. Mater. Chem., 2006, 16, 4281–4293 | 4289

ionic groups, such as 1-ethylimidazolium or lithio methano-
sulfonamido groups, on mixing, gave salts with improved
conductivity and lower Tg.223 However, as much of this work
involves in situ polymerization, as opposed to polymer
solubilization, detailed discussion is also beyond the scope of
this review.
The number of carrier ions in a gel obtained by the
polymerization224,225 of MMA in [emim][NTf2] in the presence
Published on 02 October 2006. Downloaded by Universidad de Concepcion on 2/1/2023 12:46:10 PM.
of a small amount of a cross-linker, calculated from the
Nernst–Einstein equation, was found to be greater than the
corresponding value for the ionic liquid itself. The increase in
cation transference number with decreasing concentration of
[emim][NTf2] was ascribed to interactions between the
poly(MMA) matrix and the [NTf2] anion. Addition of two
different salts, Li[NTf2] and [emim][NTf2], to poly(ethylene
oxide-co-propylene oxide) and poly(MMA) both gave single
phase amorphous materials and allowed the conventional
polyether-based system (in which ion motion is coupled with
segmental motion of the chain) to be compared with an ion gel
derived from poly(MMA) and an ionic liquid (in which such
motions are not coupled).226 Polymeric gel electrolytes,
consisting of poly(ethylene oxide)–modified poly(MMA) with
[emim][NTf2]/Mg[NTf2]2, have also been described,227,228 the
characteristics depending on the ionic liquid used.
5. Conclusions and future work
Within the broader context of solvation and solubility, the
cases of polymers as solutes and ionic liquids as solvents are
often seen as special cases. On the other hand, while ionic
liquids indeed have some unique characteristics, their beha-
viour will still be governed by the same forces that govern the
behaviour of molecular solvents.
Because of differences between ionic liquids and molecular
solvents, there is a need to refine and modify classical
approaches to the understanding of solubilization of polymers
in, and solvation of polymers by, ionic liquids. Additional
complications may arise from phenomena such as microsolva-
tion, microsegregation (micelle and emulsion formation),
plasticization and gel formation. Furthermore, dissolution of
polymers in, and phase separation from, ionic liquids may be
slow (on the timescale of several weeks) if the viscosity of
solvent or solution is high enough to represent a serious barrier
to mass and phase transfer. Such factors need to be more fully
addressed as the working lives of devices employing ionic
liquid–polymer composites may well be governed by some of
these longer term effects.
Anecdotal (though qualitative) information about the
solubility of common polymers in ionic liquids is widely
spread in the literature. There are very few studies that have
focused explicitly on the solvency of polymers in ionic liquids.
These reports reveal unexpectedly varied behaviour, indicating
that the factors responsible for polymer solubility in ionic
liquids are complex and not readily predicted. There is thus a
need for quantitative data to be more purposefully collected
and reported.
The solvency and phase behaviour of polymer–ionic liquid
mixtures thus requires more in-depth investigation. This
should include the study, or further study, of the following:
4290 | J. Mater. Chem., 2006, 16, 4281–4293
View Article Online
Specific interactions between polymers and ionic liquids
using physical techniques, such as neutron and X-ray
scattering, Raman, IR and solution and solid-state NMR,
initially using non-functionalised salts and well characterized
homopolymers.
Physical measurements on solutions of polymers in ionic
liquids in various concentration regimes, using (where appro-
priate) those conventional techniques, such as viscometry,
osmometry and light scattering, developed to study solutions
of polymers in molecular solvents.
Polymer–solvent interaction parameters from measurements
on solutions of polymers in ionic liquids and the modification
or development of appropriate models.
Computation and simulation methods applied to polymer–
solvent, particularly ionic liquid, interactions.
Acknowledgements
I thank the EPSRC for financial support (GR/N05765).
References
1 T. Welton, Chem. Rev., 1999, 99, 2071.
2 Ionic Liquids in Synthesis, ed. P. Wassercheid and T. Welton,
Wiley-VCH, Weinheim, 2003.
3 F. Andres and S. Z. El Abedin, Phys. Chem. Chem. Phys., 2006, 8,
2101.
4 C. Chiappe and D. Pieraccini, J. Phys. Org. Chem., 2005, 18, 275.
5 A. J. Carmichael and D. M. Haddleton, Ionic Liquids in Synthesis,
ed. P. Wassercheid and T. Welton, Wiley-VCH, Weinheim, 2003,
ch. 7, p. 319.
6 P. Kubisa, Prog. Polym. Sci., 2004, 29, 3.
7 P. Kubisa, J. Polym. Sci., Part A, 2005, 43, 4675.
8 D. C. Zhao, H. T. Xu, P. Xu, F. Q. Liu and G. Gao, Prog. Chem.,
2005, 17, 700.
9 F. Habrard, T. Ouisse, O. Stephan, M. Armand, M. Stark,
S. Huant, E. Dubard and J. Chevrier, J. Appl. Phys., 2004, 96,
7219.
10 K. Hettrich, S. Fischer, E. Brendler and W. Voigt, J. Appl. Polym.
Sci., 2000, 77, 2113.
11 S. Fischer, H. Leipner, K. Thümmler, E. Brendler and J. Peters,
Cellulose, 2003, 10, 227.
12 P. Snedden, A. I. Cooper, K. Scott and N. Winterton,
Macromolecules, 2003, 36, 4549.
13 K. R. Seddon, A. Stark and M. J. Torres, Pure Appl. Chem., 2000,
72, 2275.
14 J. H. Davis, Jr., C. M. Gordon, C. Hilger and P. Wasserscheid,
Ionic Liquids in Synthesis, ed. P. Wassercheid and T. Welton,
Wiley-VCH, Weinheim, 2003, ch. 1, p. 7.
15 A. E. Gebala and M. H. Jones, J. Inorg. Nucl. Chem., 1969, 31,
771.
16 R. P. Swatloski, J. D. Holbrey and R. D. Rogers, Green Chem.,
2003, 5, 361.
17 M. G. Benton and C. S. Brazel, ACS Symp. Ser., 2002, 818, 125.
18 P. Snedden, A. I. Cooper, Y. Khimyak, K. Scott and
N. Winterton, ACS Symp. Ser., 2005, 913, 133.
19 V. Strehmel, A. Laschewsky and H. Wetzel, e-Polym., 2006, 011.
20 See: N. Winterton, Ionic Liquid II, ed. H. Ohno, CHC Publishing
Co. Ltd., Tokyo, Japan, 2006, ch. 13–14, p. 138 for an earlier,
shorter version in Japanese.
21 A. R. Katritzky, D. C. Fara, H. Yang, K. Tämm, T. Tamm and
M. Karelson, Chem. Rev., 2004, 104, 175.
22 M. J. Kamlett, R. M. Doherty, J. L. M. Abboud, M. H. Abraham
and R. W. Taft, Chem.-Tech., 1986, 16, 566.
23 M. H. Abraham, Chem. Soc. Rev., 1993, 22, 73.
24 C. Reichardt, Chem. Rev., 1994, 94, 2319.
25 W. B. Harrod and N. J. Pienta, J. Phys. Org. Chem., 1990, 3, 534.
26 M. A. M. Noel, R. D. Allendoerfer and R. A. Osteryoung,
J. Phys. Chem., 1992, 96, 2391.
This journal is ß The Royal Society of Chemistry 2006

27 A. J. Carmichael and K. R. Seddon, J. Phys. Org. Chem., 2000,
13, 591.
28 M. J. Muldoon, C. M. Gordon and I. R. Dunkin, J. Chem. Soc.,
Perkin Trans. 2, 2001, 433.
29 K. A. Fletcher, I. A. Storey, A. E. Hendricks, S. Pandey and
S. Pandey, Green Chem., 2001, 3, 210.
30 S. N. Baker, G. A. Baker and F. V. Bright, Green Chem., 2002, 4,
165.
31 K. A. Fletcher and S. Pandey, Appl. Spectrosc., 2002, 56, 266.
32 R. Karmakar and A. Samanta, J. Phys. Chem. A, 2002, 106, 6670.
Published on 02 October 2006. Downloaded by Universidad de Concepcion on 2/1/2023 12:46:10 PM.
33 J. L. Anderson, J. Ding, T. Welton and D. W. Armstrong, J. Am.
Chem. Soc., 2002, 124, 14247.
34 J. G. Huddleston, G. A. Broker, H. D. Willauer and R. D. Rogers,
ACS Symp. Ser., 2002, 818, 270.
35 C. F. Poole, J. Chromatogr., A, 2004, 1037, 49.
36 W. E. Acree, Jr. and M. H. Abraham, J. Chem. Technol.
Biotechnol., 2006, 81, 1441.
37 A. Oehlke, K. Hofmann and S. Spange, New J. Chem., 2006, 30,
533.
38 G. Angelini, C. Chiappe, P. De Maria, A. Fontana, F. Gasparrini,
D. Pieraccini, M. Pierini and G. Siani, J. Org. Chem., 2005, 70,
8193.
39 T. Fujisawa, M. Fukuda, M. Terazima and Y. Kimura, J. Phys.
Chem. A, 2006, 110, 6164.
40 C. Reichardt, Green Chem., 2005, 7, 339.
41 S. K. Poole and C. F. Poole, Analyst, 1995, 120, 289.
42 D. W. Armstrong, L. He and Y.-S. Liu, Anal. Chem., 1999, 71,
3873.
43 A. W. Lantz, V. Pino, J. L. Anderson and D. W. Armstrong,
J. Chromatogr., A, 2006, 1115, 217.
44 For example: L. Crowhurst, N. L. Lancaster, J. M. Pérez Arlandis
and T. Welton, J. Am. Chem. Soc., 2004, 126, 11549 and earlier
papers.
45 A. C. Cole, J. L. Jensen, I. Ntai, K. L. T. Tran, K. J. Weaver,
D. C. Forbes and J. H. Davis, Jr., J. Am. Chem. Soc., 2002, 124,
5962.
46 N. K. Sharma, M. D. Tickell, J. L. Anderson, J. Kaar, V. Pino,
B. J. Wicker, D. W. Armstrong, J. H. Davis, Jr. and A. J. Russell,
Chem. Commun., 2006, 646.
47 B. Derecskei and A. Derecskei-Kovacs, Mol. Simul., 2006, 32,
109.
48 T. Banerjee, M. K. Singh, R. K. Sahoo and A. Khanna, Fluid
Phase Equilib., 2005, 234, 64.
49 M. Deetlefs, K. R. Seddon and M. Shara, Phys. Chem. Chem.
Phys., 2006, 8, 642.
50 D. S. Abrams and J. M. Prausnitz, AIChE J., 1975, 21, 116.
51 A. Fredenslund, R. L. Jones and J. M. Prausnitz, AIChE J., 1975,
21, 1086.
52 A. Klamt and F. Eckert, AIChE J., 2002, 48, 369.
53 M. Diedenhofen, F. Eckert and A. Klamt, J. Chem. Eng. Data,
2003, 48, 475.
54 C. Wakai, A. Oleinikova, M. Ott and H. Weingärtner, J. Phys.
Chem. B, 2005, 109, 17028.
55 F. V. Bright and G. A. Baker, J. Phys. Chem. B, 2006, 110, 5822.
56 C. Wakai, A. Oleinikova and H. Weingärtner, J. Phys. Chem. B,
2006, 110, 5824.
57 J. Wu and J. P. W. Stark, Meas. Sci. Technol., 2006, 17, 781.
58 L. Malavolta, E. Oliveira, E. M. Cilli and C. R. Nakaie,
Tetrahedron, 2002, 58, 4383.
59 J. K. Sears and J. R. Darby, The Technology of Plasticizers,
J. Wiley & Sons Ltd., Chichester, UK, 1982.
60 M. J. Kamlett, P. W. Carr, R. W. Taft and M. H. Abraham,
J. Am. Chem. Soc., 1981, 103, 6062.
61 J. Hildebrand and R. L. Scott, The Solubility of Non-Electrolytes,
3rd edn, Reinhold, New York, NY, 1950.
62 J. Hildebrand and R. L. Scott, Regular Solutions, Prentice-Hall,
Englewood Cliffs, NJ, 1962.
63 A. F. M. Barton, Handbook of Solubility Parameters and other
Cohesion Parameters, CRC Press Inc., Boca Raton, FL, 1983.
64 A. F. M. Barton, Handbook of Polymer–Liquid Parameters and
Solubility Parameters, CRC Press Inc., Boca Raton, FL, 1990.
65 C. M. Hansen, Hansen Solubility Parameters—A User’s
Handbook, CRC Press Inc., Boca Raton, FL, 1999/2000.
66 D. L. Ho and C. J. Glinka, J. Polym. Sci., Part B, 2004, 42, 4337.
This journal is ß The Royal Society of Chemistry 2006
View Article Online
67 P. L. Huyskens, M. C. Haulait-Pirson, L. D. Brandts Buys and
X. M. Van der Borght, J. Coat. Technol., 1985, 57, 57.
68 K. Swiderski, A. McLean, C. M. Gordon and D. H. Vaughan,
Chem. Commun., 2004, 2178.
69 S. H. Lee and B. B. Lee, Chem. Commun., 2005, 3469.
70 W. Xu, E. I. Cooper and C. A. Angell, J. Phys. Chem. B, 2003,
107, 6170.
71 H. W. Zhang, K. L. Hong, M. Jablonsky and J. W. Mays, Chem.
Commun., 2003, 1356.
72 A. Noda and M. Watanabe, Electrochim. Acta, 2000, 45, 1265.
73 Y. D. Liu and G. Z. Wu, Radiat. Phys. Chem., 2005, 73, 159.
74 Y. D. Liu, G. Z. Wu, D. W. Long, M. Y. Qi and Z. Y. Zhu, Nucl.
Instrum. Methods Phys. Res., Sect. B, 2005, 236, 443.
75 G. Z. Wu, Y. D. Liu and D. W. Long, Macromol. Rapid
Commun., 2005, 26, 57.
76 Y. D. Liu, G. Z. Wu, D. W. Long and G. R. Zhang, Polymer,
2005, 46, 8403.
77 C. Hardacre, J. D. Holbrey, S. P. Katdare and K. R. Seddon,
Green Chem., 2002, 4, 143.
78 M. A. Klingshirn, G. A. Broker, J. D. Holbrey, K. H. Shaughnessy
and R. D. Rogers, Chem. Commun., 2002, 1394.
79 H. Y. Ma, X. H. Wan, X. F. Chen and Q. F. Zhou, Polymer,
2003, 44, 5311.
80 H. Y. Ma, X. H. Wan, X. F. Chen and Q. F. Zhou, J. Polym. Sci.,
Part A, 2003, 41, 143.
81 S. J. Nara, J. R. Harjani, M. M. Salunkhe, A. T. Mane and
P. P. Wadgaonkar, Tetrahedron Lett., 2003, 44, 1371.
82 R. Marcilla, M. de Geus, D. Mecerreyes, C. J. Duxbury,
C. E. Koning and A. Heise, Eur. Polym. J., 2006, 42, 1215.
83 S. Harrisson, S. R. Mackenzie and D. M. Haddleton, Chem.
Commun., 2002, 2850.
84 S. Harrisson, S. R. Mackenzie and D. M. Haddleton,
Macromolecules, 2003, 36, 5072.
85 V. Strehmel, A. Laschewsky, H. Wetzel and E. Görnitz,
Macromolecules, 2006, 39, 923.
86 T. Biedron and P. Kubisa, Polym. Int., 2003, 52, 1584.
87 E. I. Lozinskaya, A. S. Shaplov and Y. S. Vygodskii, Eur. Polym.
J., 2004, 40, 2065.
88 Y. S. Vygodskii, E. L. Lozinskaya and A. S. Shaplov, Macromol.
Rapid Commun., 2002, 23, 676.
89 Y. S. Vygodskii, E. I. Lozinskaya, A. S. Shaplov, K. A. Lyssenko,
M. Y. Antipin and Y. G. Urman, Polymer, 2004, 45, 5031.
90 T. Biedron, M. Bednarek and P. Kubisa, Macromol. Rapid
Commun., 2004, 25, 878.
91 P. A. Z. Suarez, N. T. Rosa, S. Einloft, R. F. Souza and
Y. P. Dick, Polym. Bull., 1998, 41, 175.
92 H. Ma and X. Wan, ACS Symp. Ser., 2005, 913, 51.
93 H. Y. Ma, X. H. Wan, X. F. Chen and Q. F. Zhou, Chin. J.
Polym. Sci., 2003, 21, 265.
94 T. Biedron and P. Kubisa, J. Polym. Sci., Part A, 2005, 43, 3454.
95 K. Hong and J. W. Mays, ACS Symp. Ser., 2005, 913, 1.
96 V. Strehmel, A. Laschewsky, H. Kraudelt, H. Wetzel and
E. Görnitz, ACS Symp. Ser., 2005, 913, 17.
97 V. F. Smith, H. C. De Long, T. E. Sutto and P. C. Trulove, AGI—
13th Int. Symp. Molten Salts, 2002, p. 268.
98 S. Perrier, T. P. Davis, A. J. Carmichael and D. M. Haddleton,
Chem. Commun., 2002, 2226.
99 S. Perrier, T. P. Davis, A. J. Carmichael and D. M. Haddleton,
Eur. Polym. J., 2003, 39, 416.
100 J. L. Kaar, A. M. Jesionowski, J. A. Berberich, R. Moulton and
A. J. Russell, J. Am. Chem. Soc., 2003, 125, 4125.
101 J. Eastoe, S. Gold, S. E. Rogers, A. Paul, T. Welton, R. K. Heenan
and I. Grillo, J. Am. Chem. Soc., 2005, 127, 7302.
102 J. Li, J. Zhang, H. Gao, B. Han and L. Gao, Colloid Polym. Sci.,
2005, 283, 1371.
103 T. L. Merrigan, E. D. Bates, S. C. Dorman and J. H. Davis,
Chem. Commun., 2000, 2051.
104 J. L. Anderson, V. Pino, E. C. Hagberg, V. V. Sheares and
D. W. Armstrong, Chem. Commun., 2003, 2444.
105 K. A. Fletcher and S. Pandey, Langmuir, 2004, 20, 33.
106 Z. N. Wang, F. Liu, Y. Gao, W. C. Zhuang, L. M. Xu, B. X. Han,
G. Z. Li and G. Y. Zhang, Langmuir, 2005, 21, 4931.
107 H. X. Gao, J. C. Li, B. X. Han, W. N. Chen, J. L. Zhang,
R. Zhang and D. D. Yan, Phys. Chem. Chem. Phys., 2004, 6,
2914.
J. Mater. Chem., 2006, 16, 4281–4293 | 4291

108 T. Nakashima and N. Kimizuka, Chem. Lett., 2002, 1018.
109 J. Tang, D. Li, C. Sun, L. Zhen and J. Li, Colloids Surf., A, 2006,
273, 24.
110 C. Patrascu, F. Gauffre, F. Nallet, R. Bordes, J. Oberdisse, N. de
Lauth-Viguerie and C. Mingotaud, ChemPhysChem, 2006, 7, 99.
111 K. O. Evans, Colloids Surf., A, 2006, 274, 11.
112 A. Triolo, O. Russina, U. Keiderling and J. Kohlbrecher, J. Phys.
Chem. B, 2006, 110, 1513.
113 Y. He, Z. Li, P. Simone and T. P. Lodge, J. Am. Chem. Soc.,
2006, 128, 2745.
Published on 02 October 2006. Downloaded by Universidad de Concepcion on 2/1/2023 12:46:10 PM.
114 See, for example: D. Lee, J. C. Hutchison, A. M. Leone,
J. M. DeSimone and R. W. Murray, J. Am. Chem. Soc., 2002,
124, 9310.
115 L. Geng, M. L. Longmire, R. A. Reed, J. F. Parcher, C. J. Barbour
and R. W. Murray, Chem. Mater., 1989, 1, 58.
116 C. J. Barbour, R. W. Murray and J. F. Parcher, Anal. Chem.,
1991, 63, 604.
117 A. S. Harper, D. Lee, J. C. Crooker, W. Wang, M. E. Williams
and R. W. Murray, J. Phys. Chem. B, 2004, 108, 1866.
118 K. Binnemans, Chem. Rev., 2005, 105, 4148.
119 M. A. Firestone, J. A. Dzielawa, P. Zapol, L. A. Curtiss, S. Seifert
and M. L. Dietz, Langmuir, 2002, 18, 7258.
120 M. A. Firestone, P. G. Rickett, S. Seifert and M. L. Dietz, Inorg.
Chim. Acta, 2004, 357, 3991.
121 M. U. Araos and G. G. Warr, J. Phys. Chem. B, 2005, 109, 14275.
122 D. F. Evans, S.-H. Chen, G. W. Schriver and E. M. Arnett, J. Am.
Chem. Soc., 1981, 103, 481.
123 L. Y. Wang, X. Chen, Y. C. Chai, J. C. Hao, Z. M. Sui,
W. C. Zhuang and Z. W. Sun, Chem. Commun., 2004, 2840.
124 K. Hoshino, M. Yoshio, T. Mukai, K. Kishimoto, H. Ohno and
T. Kato, J. Polym. Sci., Part A, 2003, 41, 3486.
125 Polyelectrolytes, ed. M. Hara, CRC Press Inc., Boca Raton, FL,
1992.
126 J. Korkisch, Handbook of Ion Exchange Resins and their
Applications, CRC Press, Boca Raton, FL, 1988.
127 K. A. Mauritz and R. B. Moore, Chem. Rev., 2004, 104, 4535.
128 M. Watanabe, S. Yamada, K. Sanui and N. Ogata, J. Chem. Soc.,
Chem. Commun., 1993, 929.
129 M. Watanabe, S. Yamada and N. Ogata, Electrochim. Acta, 1995,
40, 2285.
130 N. Ogata, K. Sanui, M. Rikukawa, S. Yamada and M. Watanabe,
Synth. Met., 1995, 69, 521.
131 R. Marcilla, F. Alcaide, H. Sardon, J. A. Pomposo, C. Pozo-
Gonzalo and D. Mecerreyes, Electrochem. Commun., 2006, 8, 482.
132 R. Marcilla, J. A. Blazquez, R. Fernandez, H. Grande,
J. A. Pomposo and D. Mecerreyes, Macromol. Chem. Phys.,
2005, 206, 299.
133 R. Marcilla, J. A. Blazquez, R. Fernandez, J. A. Pomposo and
D. Mecerreyes, J. Polym. Sci., Part A, 2004, 42, 208.
134 P. Wang, S. M. Zakeeruddin, I. Exnar and M. Grätzel, Chem.
Commun., 2002, 2972.
135 K. Suzuki, M. Yamaguchi, S. Hotta, N. Tanabe and S. Yanagida,
J. Photochem. Photobiol., A, 2004, 164, 81.
136 P. J. Flory, J. Chem. Phys., 1941, 9, 660.
137 M. L. Huggins, J. Chem. Phys., 1941, 9, 440.
138 I. Teraoka, Polymer Solutions: An Introduction to Physical
Properties, John Wiley & Sons, Inc., New York, 2002.
139 R. A. Orwoll, Rubber Chem. Technol., 1977, 50, 451.
140 (a) T. Iwatsubo, T. Masuoka and K. Mizoguchi, J. Polym. Sci.,
Part B, 1994, 32, 7; (b) Y. Einaga, Prog. Polym. Sci., 1994, 19, 1.
141 T. Hino and J. M. Prausnitz, J. Appl. Polym. Sci., 1998, 68, 2007.
142 A. P. Safronov and A. Yu. Zubarev, Polymer, 2002, 43, 743.
143 M. Watanabe and T. Mizumura, Solid State Ionics, 1996, 86–88,
353.
144 J. S. Wilkes, P. J. Castle, R. Schoske, C. J. Humphrey, F. B. Layo
and R. Slanger, AGI—12th Int. Symp. Molten Salts, 2000, p. 6565.
145 M. Forsyth, S. Jiazeng and D. R. MacFarlane, Electrochim. Acta,
2000, 45, 1249.
146 T. Biedron and P. Kubisa, J. Polym. Sci., Part A, 2002, 40, 2799.
147 A. Lewandowski and A. Swiderska, Pol. J. Chem., 2004, 78, 1371.
148 A. Lewandowski and A. Swiderska, Solid State Ionics, 2004, 169,
21.
149 J. D. Holbrey, J. Chen, M. B. Turner, R. P. Swatloski, S. K. Spear
and R. D. Rogers, ACS Symp. Ser., 2005, 913, 71.
4292 | J. Mater. Chem., 2006, 16, 4281–4293
View Article Online
150 T. Kawauchi, J. Kumaki, K. Okoshi and E. Yashima,
Macromolecules, 2005, 38, 9155.
151 P. V. Wright, MRS Bull., 2002, 27, 597.
152 E. Marwanta, T. Mizumo, N. Nakamura and H. Ohno, Polymer,
2005, 46, 3795.
153 T. Fukushima, A. Kosaka, Y. Ishimura, T. Yamamoto,
T. Takigawa, N. Ishii and T. Aida, Science, 2003, 300, 2072.
154 T. Fukushima, A. Kosaka, Y. Yamamoto, T. Aimiya,
S. Notazawa, T. Takigawa, T. Inabe and T. Aida, Small, 2006,
2, 554.
155 K. Hanabusa, H. Fukui, M. Susuki and H. Shirai, Langmuir,
2005, 21, 10383.
156 N. Kimizuka and T. Nakashima, Langmuir, 2001, 17, 6759.
157 H. Sawada, K. Shima, J. Kyokane, K. Oharu, H. Nakagawa and
T. Kitazume, Eur. Polym. J., 2004, 40, 1595.
158 M. A. Klingshirn, S. K. Spear, J. D. Holbrey, J. G. Huddleston
and R. D. Rogers, ACS Symp. Ser., 2005, 913, 149.
159 L. T. Costa and M. C. C. Ribeiro, J. Chem. Phys., 2006, 124,
184902.
160 S. Samitsu, J. Araki, T. Kataoka and K. Ito, J. Polym. Sci.,
Part B, 2006, 44, 1985.
161 M. Erbeldinger, A. J. Mesiano and A. J. Russell, Biotechnol.
Prog., 2000, 16, 1129.
162 H. Vallette, L. Ferron, G. Coquerel, F. Guillen and
J.-C. Plaquevent, ARKIVOC, 2006, 200.
163 W. Miao and T.-H. Chan, J. Org. Chem., 2005, 70, 3251.
164 Y. Patell, K. R. Seddon, L. Dutta and A. Fleet, NATO ASI Ser.,
Ser. II, 2003, 92, 499.
165 H. Ohno and N. Nishimura, J. Electrochem. Soc., 2001, 148,
E168.
166 M. Hirao, K. Ito and H. Ohno, Electrochim. Acta, 2000, 45, 1291.
167 M. Hirao, H. Sugimoto and H. Ohno, J. Electrochem. Soc., 2000,
147, 4168.
168 N. Nishimura and H. Ohno, J. Mater. Chem., 2002, 12, 2299.
169 N. Nishimura, Y. Nomura, N. Nakamura and H. Ohno,
Biomaterials, 2005, 26, 5558.
170 R. P. Swatloski, S. K. Spear, J. D. Holbrey and R. D. Rogers,
J. Am. Chem. Soc., 2002, 124, 4974.
171 C. Graenacher, US Pat. 1 943 176, 1934.
172 S. A. Forsyth, D. R. MacFarlane, R. J. Thomson and M. von
Itzstein, Chem. Commun., 2002, 714.
173 Q. Liu, M. H. A. Janssen, F. van Rantwijk and R. A. Sheldon,
Green Chem., 2005, 7, 39.
174 S. Fischer, K. Thummler, K. Pfeiffer, T. Liebert and T. Heinze,
Cellulose, 2002, 9, 293.
175 J. L. Anderson, J. Ding, T. Welton and D. W. Armstrong, J. Am.
Chem. Soc., 2002, 124, 14247.
176 R. C. Remsing, R. P. Swatloski, R. D. Rogers and G. Moyna,
Chem. Commun., 2006, 1271.
177 D. M. Phillips, L. F. Drummy, R. R. Naik, H. C. De Long,
D. M. Fox, P. C. Trulove and R. A. Mantz, Chem. Commun.,
2005, 4206.
178 H. B. Xie, S. H. Li and S. B. Zhang, Green Chem., 2005, 7, 606.
179 R. P. Swatloski and R. D. Rogers, US Pat. 2 003 157 351, 2003.
180 News release, BASF, 8 March 2006: P. L. Short, Chem. Eng.
News, 2006, 84, 15.
181 S. N. Baker, T. M. McCleskey, S. Pandey and G. A. Baker, Chem.
Commun., 2004, 940.
182 K. Fujita, D. R. MacFarlane and M. Forsyth, Chem. Commun.,
2005, 4804.
183 H. Ohno, C. Suzuki and K. Fujita, Electrochim. Acta, 2006, 51,
3685.
184 H. Zhao, O. Olubajo, Z. Song, A. L. Sims, T. E. Person,
R. A. Lawal and L. A. Holley, Bioorg. Chem., 2006, 34, 15.
185 W. R. Carper, A. Dölle, C. C. Hanke, C. Hardacre, A. Leuchter,
R. M. Lynden-Bell, Z. Meng, G. Palmer and J. Richter, Ionic
Liquids in Synthesis, ed. P. Wassercheid and T. Welton, Wiley-
VCH, Weinheim, 2003, ch. 4, p. 127.
186 C. M. Stancik, A. R. Lavoie, J. Schutz, P. A. Achurra, P. Lindner,
A. P. Gast and R. M. Waymouth, Langmuir, 2004, 20, 596.
187 J. S. Mouthrop, R. P. Swatlowski, G. Moyna and R. D. Rogers,
Chem. Commun., 2005, 1557.
188 T. Heinze, K. Schwikal and S. Barthel, Macromol. Biosci., 2005,
5, 520.
This journal is ß The Royal Society of Chemistry 2006

189 Z. Tingting, W. Huaping, W. Biao, T. Xiaoping, Z. Yumei and
J. Jianming, Polym. Bull., 2006, 57, 369.
190 X. P. Tu, Y. M. Zhang, T. T. Zhao and H. P. Wang, J. Macromol.
Sci., Part B, 2006, 45, 665.
191 R. A. Mantz, H. C. De Long, R. A. Osteryoung and P. C. Trulove,
AGI—12th Int. Symp. Molten Salts, 2000, p. 169.
192 R. A. Mantz, T. E. Sutto, H. C. De Long and P. C. Trulove,
AGI—13th Int. Symp. Molten Salts, 2002, p. 94.
193 T. Schäfer, R. E. Di Paolo, R. Franco and J. G. Crespo, Chem.
Commun., 2005, 2594.
Published on 02 October 2006. Downloaded by Universidad de Concepcion on 2/1/2023 12:46:10 PM.
194 S. J. Pas, J. M. Pringle, M. Forsyth and D. R. MacFarlane, Phys.
Chem. Chem. Phys., 2004, 6, 3721.
195 W. E. Gardinier, G. A. Baker, S. N. Baker and F. V. Bright,
Macromolecules, 2005, 38, 8574.
196 M. P. Scott, M. Rahman and C. S. Brazel, Eur. Polym. J., 2003,
39, 1947.
197 M. P. Scott, M. G. Benton, M. Rahman and C. S. Brazel, ACS
Symp. Ser., 2003, 856, 468.
198 M. P. Scott, C. S. Brazel, M. G. Benton, J. W. Mays, J. D. Holbrey
and R. D. Rogers, Chem. Commun., 2002, 1370.
199 M. Rahman, H. W. Shoff and C. S. Brazel, ACS Symp. Ser.,
2005, 913, 913.
200 A. Lewandowski and A. Swiderska, Solid State Ionics, 2003, 161,
243.
201 K. Kowalczyk and T. Spychaj, Polimery, 2003, 48, 833 (in Polish).
202 F. M. Gray, Solid Polymer Electrolytes, VCH Publishers,
New York, 1991.
203 S. S. Zhang, Z. Chang, K. Xu and C. A. Angell, Electrochim.
Acta, 2000, 45, 1229.
204 J. Fuller, A. C. Breda and R. T. Carlin, J. Electrochem. Soc.,
1997, 144, L67.
205 J. Fuller, A. C. Breda and R. T. Carlin, J. Electroanal. Chem.,
1998, 459, 29.
206 C. Tiyapiboonchaiya, D. R. MacFarlane, J. Z. Sun and
M. Forsyth, Macromol. Chem. Phys., 2002, 203, 1906.
207 C. Tiyapiboonchaiya, J. M. Pringle, D. R. MacFarlane,
M. Forsyth and J. Z. Sun, Macromol. Chem. Phys., 2003, 204,
2147.
208 T. E. Sutto, H. C. De Long and P. C. Trulove, Z. Naturforsch., A,
2002, 57, 839.
This journal is ß The Royal Society of Chemistry 2006
View Article Online
209 T. E. Sutto, H. C. De Long and P. C. Trulove, AGI—13th Int.
Symp. Molten Salts, 2002, p. 134.
210 H. C. De Long, P. C. Trulove and T. E. Sutto, ACS Symp. Ser.,
2003, 856, 478.
211 S.-H. Yeon, K.-S. Kim, S. Choi, J.-H. Cha and H. Lee, J. Phys.
Chem. B, 2005, 109, 17928.
212 B. Singh and S. S. Sekhon, Chem. Phys. Lett., 2005, 414, 34.
213 B. Singh and S. S. Sekhon, J. Phys. Chem. B, 2005, 109, 16539.
214 D. Bansal, F. Cassel, F. Croce, M. Hendrickson, E. Plichta and
M. Salomon, J. Phys. Chem. B, 2005, 109, 4492.
215 K.-S. Kim, S.-Y. Park, S.-H. Yeon and H. Lee, Electrochim. Acta,
2005, 50, 5673.
216 M. Doyle, S. K. Choi and G. Proulx, J. Electrochem. Soc., 2000,
147, 34.
217 S. S. Sekhon, B. S. Lalia, J.-S. Park, C.-S. Kim and K. Yamada,
J. Mater. Chem., 2006, 16, 2256.
218 D. M. Tigelaar, J. R. Waldecker, K. M. Peplowski and
J. D. Kinder, Polymer, 2006, 47, 4269.
219 S. Mitsushima, R. Sakamoto, K. Kudo, Y. Takeoka, N. Kamiya
and K. I. Ota, J. New Mater. Electrochem. Syst., 2005, 8, 77.
220 C. A. Angell, C. Liu and E. Sanchez, Nature, 1993, 362, 137.
221 M. D. Ingram, C. T. Imrie, Z. Stoeva, S. J. Pas, K. Funke and
H. W. Chandler, J. Phys. Chem. B, 2005, 109, 16567.
222 J. H. Kim, B. R. Min, J. Won and Y. S. Kang, J. Phys. Chem. B,
2003, 107, 5901.
223 H. Ohno, Y. Nakai and K. Ito, Chem. Lett., 1998, 15.
224 M. A. Susan, T. Kaneko, A. Noda and M. Watanabe, J. Am.
Chem. Soc., 2005, 127, 4976.
225 Md. A. B. H. Susan, A. Nada and M. Watanabe, ACS Symp.
Ser., 2005, 913, 119.
226 S. Seki, A. B. H. Susan, T. Kaneko, H. Tokuda, A. Noda and
M. Watanabe, J. Phys. Chem. B, 2005, 109, 3886.
227 N. Yoshimoto, T. Shirai and M. Morita, Electrochim. Acta, 2005,
50, 3866.
228 M. Morita, T. Shirai, N. Yoshimoto and M. Ishikawa, J. Power
Sources, 2005, 139, 351.
229 P. Wasserscheid, M. Sesing and W. Korth, Green Chem., 2002, 4,
134.
230 A. A. Aerov, A. R. Khokhlov and I. I. Potemkin, J. Phys. Chem.
B, 2006, 110, 16205.
J. Mater. Chem., 2006, 16, 4281–4293 | 4293