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Synthesis and characterization of amphiphilic

diblock copolymers of 2-(1-imidazolyl)ethyl
Cite this: Polym. Chem., 2014, 5, 4339
methacrylate and styrene
Maria Rikkou-Kalourkoti, Panayiota A. Panteli and Costas S. Patrickios*

Received 15th February 2014
Accepted 24th March 2014
DOI: 10.1039/c4py00221k
www.rsc.org/polymers
Six amphiphilic diblock copolymers based on the hydrophilic monomer 2-(1-imidazolyl)ethyl methacrylate
(ImEMA) and the hydrophobic monomer styrene (Sty) were prepared by sequential reversible addition
fragmentation chain transfer (RAFT) polymerization. RAFT polymerization was performed via the use of
4-cyano-4-(dodecylsulfanylthiocarbonylsulfanyl)pentanoic acid (CDP) as the chain transfer agent and
glacial acetic acid as the solvent. Amphiphilic diblock copolymers with a range of compositions were
prepared, with ImEMA rst blocks of constant (nominal) degree of polymerization (DP) equal to 100, and
Sty second blocks of a DP between 18 and 482, having ImEMA contents between 15 and 80 mol%, as
measured by 1H NMR spectroscopy in CDCl3. Only the Sty-rich ($51 mol%) diblock copolymers were
fully soluble in the solvent for gel permeation chromatography (GPC), tetrahydrofuran; GPC analysis of
these copolymers indicated molecular weights in the range of 15 to 34 kDa, and molecular weight
dispersities ranging from 1.1 to 1.6. At room temperature, the side-group of the ImEMA units was stable
in an acidic environment but hydrolyzed slowly under alkaline conditions. In bulk neutral samples, the
ImEMA side-group was thermally stable up to
250  C. Finally, dynamic light scattering and polarized
light microscopy indicated that the Sty-rich diblock copolymers formed spherical micelles in chloroform,
whereas all diblock copolymers formed anisotropic nanophases in water.

N-isopropylacrylamide8 and amphiphilic diblock copolymers

Introduction
Imidazole is a heterocyclic aromatic molecule bearing two
nitrogen atoms, conferring to it high polarity.13 The imidazole
ring has great biological importance, appearing in many bio-
logical molecules including the side-group of histidine which is
the main component of histones, and is part of the serine
catalytic triad found in a certain type of proteases.4 Because of
its biological importance, the imidazole ring has been intro-
duced in many types of synthetic polymers, including
vinylics,13,510 methacrylates1115 and styrenics.16 Apart from the
polymerization of monomers bearing neutral imidazole side-
groups, the polymerization of monomers with pendant imida-
zolium salts has also been reported and currently receives great
attention because of their action as ionic liquids.1722
In most cases, imidazole has been introduced via its vinylic
monomers, such as N-vinylimidazole (NVIm) or 4-vinyl-
imidazole (4VIm). For example, NVIm was used for the prepa-
ration of its linear homopolymers,3 its amphiphilic random
copolymers with ethyl methacrylate (EMA),5 and its randomly-
crosslinked amphiphilic copolymer conetworks with poly-
(tetrahydrofuran)6,7 using free radical polymerization, as well as
the preparation of double-hydrophilic diblock copolymers with
Department of Chemistry, University of Cyprus, P. O. Box 20537, 1678 Nicosia, Cyprus.
E-mail: kalourk@ucy.ac.cy; ppante02@ucy.ac.cy; costasp@ucy.ac.cy
with styrene10 using reversible additionfragmentation chain
transfer (RAFT) polymerization. Regarding the other vinylic
imidazole-containing monomers, Long et al. reported the use of
4VIm2,9 for the synthesis of linear homopolymers and diblock
and ABA triblock copolymers with di(ethylene glycol)methyl
ether methacrylate,9 using RAFT polymerization. There is also
one example of a styrenic imidazole-containing monomer used
for the preparation of random copolymers with n-butyl acrylate
using nitroxide-mediated radical polymerization (NMP).16
Additionally, imidazole-containing methacrylate monomers
have also been prepared and polymerized. In particular, 2-[(1-
imidazolyl)formyloxy]ethyl methacrylate was used for the
preparation of its homopolymers,11 and 2-(1-imidazolyl)ethyl
methacrylate (ImEMA) was used for the preparation of its
homopolymers,12 its double-hydrophilic diblock copolymers
with 2-(dimethylamino)ethyl methacrylate,13 its ampholytic
diblock copolymers with methacrylic acid,15 and its end-linked
homopolymer networks,14 by free radical polymerization11 and
group transfer polymerization (GTP).1215 Finally, imidazole-
bearing (co)polymers were recently prepared by Lowe and
coworkers23 via a polymer modication strategy, and, in partic-
ular, through the acyl substitution reaction of penta-
uorophenyl acrylate units with histamine [2-(1H-imidazol-4-yl)-
ethanamine]. Herein, we report for the rst time the use of
ImEMA for the synthesis of its amphiphilic diblock copolymers

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Polymer Chemistry
with styrene using RAFT polymerization, and the investigation
of the resulting materials in terms of their thermal and hydro-
lytic stability, and their self-assembly properties.
Experimental section
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Materials and methods
All chemical reagents used in this investigation were purchased
from Aldrich, Germany, whereas all solvents, including
deuterated solvents, i.e., deuterated chloroform (CDCl3, 99.8%)
and deuterated dimethylsulfoxide (d6-DMSO, 99.9%), were
purchased from Merck, Germany. An exception was tetrahy-
drofuran (THF, 99.8%) which was purchased from Labscan
analytical science, Ireland. For the synthesis of the ImEMA
monomer, which is not commercially available, the reagents
imidazole (99%), ethylene carbonate (98%), methacryloyl chlo-
ride (97%), triethylamine ($99%), hydrochloric acid (37%),
potassium carbonate (99.99%), calcium hydride (9095%),
toluene (99.9%), chloroform (>99%), N,N-dimethylformamide
(DMF, 99.8%), and THF (99%) were used. Triethylamine was
stirred over calcium hydride for at least 3 days and vacuum-
distilled just prior to use. Methacryloyl chloride was vaccum-
distilled before use, whereas the other reagents were used as
received.
For the synthesis of the ImEMA polymers, 4,40 -azobis(4-cya-
novaleric acid) (V-501, $98%) was used as the initiator, 4-cyano-
4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid (CDP,
97%) was used as the chain transfer agent, and glacial acetic
acid (AcOH, 100%) was used as the solvent. However, initial
polymerization experiments utilized 2-azobis(isobutylnitrile)
(AIBN, 98%) and 2-cyano-2-propyl benzodithioate (CPB, >97%)
as the initiator and the chain transfer agent, respectively. For
the preparation of the amphiphilic diblock copolymers, styrene
(Sty, >99%) was used as the second monomer. For its purica-
tion, styrene was rst passed through a basic alumina column
and was subsequently stirred over calcium hydride to remove
the last traces of moisture and protic impurities in the presence
of added 2,2-diphenyl-1-picrylhydrazyl hydrate (DPPH, 95%)
free-radical inhibitor, and was stored in the refrigerator at about
5  C. Finally, the styrene was freshly distilled under vacuum just
before its use and was kept under a dry argon atmosphere.
Synthesis of the ImEMA monomer
ImEMA was prepared in two stages. In the rst stage, 26 g (0.38
mol) of imidazole and 52 g (0.59 mol) of ethylene carbonate
were weighed and transferred to a 250 mL round-bottomed
ask containing 100 mL of toluene, which was reuxed (110  C)
for 6 h. Subsequently, the mixture was allowed to cool down to
room temperature. This led to the formation of two layers, of
which the toluene top layer was removed. In the remaining
aqueous bottom layer, concentrated HCl was added, and the
mixture was washed three times with CHCl3. The aqueous top
layer was collected, and potassium carbonate (200 g, 1.45 mol)
was added to it. The aqueous mixture was washed three times
with CHCl3 (3  200 mL). The organic phase was then collected
and dried using anhydrous MgSO4. CHCl3 was evaporated
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under vacuum from the solution, and 24.29 g (0.217 mol)
2-imidazol-1-yl-ethanol (ImEOH) was isolated as orange oil in
56.7% yield.
In the second and nal stage of monomer synthesis, 24.29 g
(0.217 mol) ImEOH was reacted with 25.4 mL methacryloyl
chloride (27.17 g, 0.260 mol) in the presence of 181.28 mL Et3N
(131.52 g, 1.30 mol) in 140 mL CHCl3 at 0  C. The mixture was
le under stirring for 5 h and was stored in the refrigerator
overnight. On the next day, the mixture was ltered to remove
the triethylamine hydrochloride salt which was formed, and the
solution was passed twice through a basic alumina column to
remove methacrylic acid which is the hydrolysis product of
excess methacryloyl chloride. Aer that, CHCl3 and Et3N were
removed using a rotary evaporator. Subsequently, the isolated
monomer was stirred over calcium hydride and the DPPH
inhibitor for one day. Finally, the monomer was vacuum-
distilled at 118  C and was isolated as a yellow liquid in a yield
of 38.7%. The chemical structures of ImEOH and ImEMA were
conrmed by 1H NMR spectroscopy.
RAFT polymerization
Synthesis of the ImEMA homopolymers. A solution of
ImEMA (1.00 g, 5.55 mmol), CDP chain transfer agent (22.4 mg,
5.55  105 mol) and V-501 radical initiator (15.6 mg, 5.55 
105 mol) in 5.54 mL glacial acetic acid (5.81 g, 96.8 mmol) was
transferred to a 50 mL round-bottomed ask tted with a glass
valve and containing a magnetic stirring bar. The system was
degassed by three freezepumpthaw cycles, and was subse-
quently placed in an oil bath thermostatted at 70  C for 20 h.
Synthesis of the amphiphilic diblock copolymers. Amphi-
philic diblock copolymers of dierent compositions were
prepared via sequential RAFT polymerization. In all cases, the
degree of polymerization (DP) of the ImEMA rst block was
constant and equal to 100, while the DP of the Sty second block
was varied between 18 and 482. For example, for the synthesis of
ImEMA92-b-Sty25, a solution of ImEMA (1.00 g, 5.55 mmol), CDP
chain transfer agent (22.4 mg, 5.55  105 mol) and V-501
radical initiator (15.6 mg, 5.55  105 mol) in 5.54 mL glacial
acetic acid (5.81 g, 96.8 mmol) was transferred to a 50 mL
round-bottomed ask tted with a glass valve and containing a
magnetic stirring bar. The system was degassed by three freeze
pumpthaw cycles, and was subsequently placed in an oil bath
thermostatted at 70  C for 20 h, allowing monomer conversion
to reach 90%. Subsequently, 0.16 mL Sty (0.15 g, 1.39  103
mol) was transferred to the ask and was le to react for 20 h
(Sty conversion 27.7%) to form the desired diblock copolymer.
Examination of polymer thermal and hydrolytic stability
Thermolysis of the ImEMA homopolymer. The kinetics of the
thermolysis of an ImEMA homopolymer at 110  C in a vacuum
oven was investigated. To this end, thirteen samples (
0.05 g
each) of ImEMA100 were transferred into glass vials and were
placed in a vacuum oven kept at 110  C for 3 days. Samples were
taken out of the vacuum oven at dierent times during thermol-
ysis, and were characterized by 1H NMR spectroscopy to calculate
the extent of thermolysis and identify the thermolysis products.
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Alkaline hydrolysis of the ImEMA homopolymer. 0.02 g of
ImEMA100 and 40 mL of NaOD (40% wt in D2O) were transferred
and dissolved in 0.6 mL of a mixture composed of d6-DMSO and
d4-methanol (60 : 40). The resulting solution (nal NaOD
concentration 0.67 M) was transferred into a 25 mL round-
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bottomed ask containing a magnetic stirring bar, and was
allowed to react at room temperature. Samples were taken out
of the reaction mixture at dierent times during hydrolysis and
were characterized by 1H NMR spectroscopy to estimate the
extent of the reaction.
Acid hydrolysis of the ImEMA homopolymer. 0.02 g of
ImEMA100 and 40 mL of DCl (10 M in D2O) were transferred and
dissolved in 0.6 mL of d6-DMSO. The resulting solution (nal
DCl concentration 0.67 M) was transferred into a 25 mL
round-bottomed ask containing a magnetic stirring bar, and
was allowed to react at room temperature. Samples were taken
out of the reaction mixture at dierent times for 2 days and were
characterized by 1H NMR spectroscopy.
Polymer characterization
Gel permeation chromatography. The molecular weight
distributions (MWDs) of all the THF-soluble polymers were
recorded by gel permeation chromatography (GPC), from which
the number-average molecular weights, Mn, the weight-average
molecular weights, Mw, and the molecular weight dispersities
( Mw/Mn) were calculated. A single Polymer Laboratories PL-
Mixed D column (bead size 5 mm; pore sizes 100, 500, 103 immersion, but not dissolution. Each sample was subsequently
and 104 A) was used for the analyses. The mobile phase was
THF, which was delivered using a Waters 515 isocratic pump at
a ow rate of 1 mL min1. The refractive index (RI) signal was
measured using a Polymer Laboratories ERC-7515A RI detector.
The calibration curve was based on ten narrow molecular
weight (800, 2200, 6370, 12 600, 23 500, 41 400, 89 300, 201 000,
392 000 and 675 000 g mol1) linear poly(methyl methacrylate)
(polyMMA) standards from Polymer Standards Service.
NMR spectroscopy. A 500 MHz Avance Bruker spectrometer
equipped with an Ultrashield magnet was used to acquire the
1
H NMR spectra of all the (co)polymers, their degradation
products (upon their thermolysis or alkaline hydrolysis), and all
the newly-synthesized low-molecular-weight compounds,
ImEOH and ImEMA. In most cases, CDCl3 was used as the NMR
solvent; however, the more polar d6-DMSO was employed for
analyzing the thermolyzed and hydrolyzed polymers.
DSC. Dierential scanning calorimetry (DSC) was performed
using a Thermal Analysis Instruments (TA) dierential scan-
ning calorimeter model Q1000, covering the temperature range
from 40 to 350  C (or to 220  C) at 10  C min1. Sample amounts
of 0.52.0 mg were prepared in hermetically-sealed DSC pans.
TGA. Thermal gravimetric analysis (TGA) was performed on a
TA thermogravimetric analyzer model Q500, covering the
temperature range from 40 to 600  C at 10  C min1. Sample
amounts of around 10 mg were loaded in ceramic TGA pans.
Hydrogen ion titration. Aqueous solutions of the ImEMA
homopolymer and the amphiphilic diblock copolymers (6 g of a
1% w/w solution) were titrated in the pH range from 2 to 12,
using a 0.5 M NaOH standard solution. The pH of the solution
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was measured using a Corning PS30 portable pH-meter. The
(co)polymer solutions turned cloudy and precipitated upon
increasing the pH; the precipitation pH was noted. Further-
more, the eective pK of the ImEMA units was estimated as the
pH at 50% ionization.
Dynamic light scattering (DLS). The hydrodynamic diame-
ters of the synthesized amphiphilic diblock copolymers in
chloroform were measured by dynamic light scattering (DLS).
Copolymer solutions (1% w/w) were prepared by dissolving an
appropriate amount of polymer in chloroform, and were ltered
three times through PTFE syringe lters with a pore diameter of
0.45 mm. The ltered solutions were le to settle for about an
hour, so that any air bubbles could escape before the DLS
measurement. A 90Plus Brookhaven DLS spectrophotometer,
equipped with a BI9000 correlator and a 30 mW red diode laser
emitting at 673 nm, was used to determine the intensity of the
scattered light at an angle of 90 . The data were processed using
multimodal size distribution (MSD) analysis based on non-
negatively constrained least squares (NNCLS).
Polarized light microscopy. All polymers were examined for
birefringence by polarized light microscopy. To this end, each
solid sample was carefully crushed to a ne powder and a small
amount was examined under both parallel and crossed polar-
izers using a Leica DM LSP polarized light microscope, at an
overall magnication of 100, and an object eld of the order of
0.5 mm. Following these observations, a drop of water was
added on top of each solid sample, leading to its complete
examined using the same magnication as for the dry sample.
The examination was performed at room temperature (roughly
at 20  C) without temperature control.
Results and discussion
ImEMA monomer
For the preparation of the amphiphilic diblock copolymers, it
was rst necessary to synthesize 2-(1-imidazolyl)ethyl methac-
rylate (ImEMA), the imidazole-containing monomer, which was
prepared in two stages, according to the literature.12 In the rst
stage, imidazole was reacted with
50% excess ethylene
carbonate, and the reaction was followed by 1H NMR spectros-
copy, until all imidazole was consumed. When the reaction was
completed, two phases were formed. Then, the toluene top layer
was removed and the remaining aqueous bottom layer, con-
taining the product (ImEOH), was washed three times with
chloroform. Subsequently, the excess of ethylene carbonate
transferred (together with the ImEOH product) to chloroform
was neutralized by the addition of fuming HCl to produce
ethylene glycol and carbon dioxide. Following that, remaining
HCl was neutralized by the addition of a pre-calculated amount
of K2CO3. The mixture was then extracted again three times with
chloroform. Aer solvent evaporation, the product was isolated
and characterized via 1H NMR spectroscopy. The yield of the
reaction was 56.7% and was higher than that reported previ-
ously.12 In the second stage, an esterication reaction was per-
formed between the product of the rst stage (ImEOH) and
methacryloyl chloride in the presence of Et3N in absolute THF.
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Fig. 1 presents the two chemical reactions employed for the
preparation of ImEMA, whereas Fig. 2 displays the 1H NMR
spectra of the ImEMA monomer and the ImEOH intermediate.
ImEMA was obtained as a yellowish oil with a yield of 38.7%,
a lower value than that reported before,12 and was characterized
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via 1H NMR spectroscopy; the 1H NMR spectrum of ImEMA is
shown in Fig. 2, next to that of ImEOH.
ImEMA homopolymers
For the synthesis of the ImEMA homopolymers, RAFT poly-
merization2427 was chosen, which is a quasiliving28 polymeri-
zation method ensuring relatively narrow molecular weight
distributions. For successful preparation, it is necessary to nd
a suitable polymerization system and conditions. Initially, 2,20 -
azobis(isobutylnitrile) (AIBN) was chosen as the initiator (I), 2-
cyano-2-propyl benzodithioate (CPB) served as the chain trans-
fer agent (CTA), and DMF was employed as the solvent. When
the monomer concentration was 7.0 M and the [I]/[CTA] molar
ratio was 0.625, a covalent polymer network (persisting disso-
lution upon acetic acid addition) was formed instead of a
soluble linear polymer, manifesting polymer chain interlinking
through undesired chemical bonds. To avoid network forma-
tion, lower monomer concentrations were subsequently tested,
3.0, 4.5 and 6.0 M. Only the polymerization with the lowest
monomer concentration, 3.0 M, resulted in a soluble product;
however, the monomer conversion was very low,
10%, even
aer 3 days of polymerization. Formation of networks instead of
linear soluble polymers prevented homogeneous polymeriza-
tion in organic media such as DMF.2 As this result was not
satisfactory, a dierent initiator, chain transfer agent and
solvent were tested. Thus, following Long et al.,2 the polymeri-
zation reactions were performed using glacial acetic acid as the
Fig. 1 Two-step synthesis of 2-(1-imidazolyl)ethyl methacrylate
(ImEMA) from imidazole, ethylene carbonate, and methacryloyl
chloride.
1
Fig. 2 H NMR spectra of ImEOH and ImEMA in CDCl3.
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solvent, CDP as the chain transfer agent and V-501 as the
initiator. With this polymerization system, the ImEMA homo-
polymers were prepared successfully, without gel formation.
Thus, this polymerization system was employed for the
synthesis of both the ImEMA homopolymers and the amphi-
philic ImEMASty diblock copolymers. Table 1 summarizes all
the tests performed for optimizing the preparation of the
ImEMA homopolymers.
ImEMASty diblock copolymers
For the preparation of the amphiphilic diblock copolymers,
much eort was initially made to synthesize them via step-wise
polymerization, i.e., by isolating the original ImEMA homo-
polymer. In the rst attempt, the isolated (by precipitation and
drying) ImEMA homopolymer was used as a macroinitiator for
the polymerization of Sty in the bulk at 120  C where thermal
polymerization of Sty takes place. However, this led to network
formation, manifesting undesired covalent chain interlinking.
In the second attempt, also performed in the absence of the
polymerization solvent, a few drops of concentrated AcOH were
added to keep the imidazole ring ionized. In this case, some Sty
was polymerized, apparently via conventional free radical
polymerization, as solubility tests indicated the presence of
homopolymers of both Sty and ImEMA, but not of their diblock
copolymer.
For the above reasons, the synthesis of the ImEMASty
diblock copolymers was subsequently pursued via sequential
rather than step-wise polymerization. Thus, ImEMA was poly-
merized rst up to a conversion of
90% and then Sty was
added, in one case with and in another without DMF (as
solvent). The presence of DMF was initially considered to be
necessary in order to help the dissolution of the formed polySty.
To our surprise, the conversion of Sty to polymer was extremely
low,
1%, when DMF was added (possibly due to the dilution
eected by the DMF addition), whereas successful polymeriza-
tion of Sty, o the end of the polyImEMA macroinitiator, took
place in the absence of added DMF. Fig. 3 shows the experi-
mental procedure followed for the synthesis of the ImEMASty
amphiphilic diblock copolymers. Six diblock copolymers were
prepared in total. The (nominal) degree of polymerization (DP)
of ImEMA in the copolymers was kept constant and equal to
100, while the DP of the Sty block was varied, resulting in
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Table 1 Results of polymerization reactions performed for the optimization of the synthesis of the ImEMA homopolymers

Polymerization Monomer Monomer

Polymer time (h) Initiator CTA [I]/[CTA] Solvent concentration (M) conversion

PP1 48 AIBN CPB 0.625 DMF 7.0 Network

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PP2 24 AIBN CPB 0.624 DMF 6.0 Network

PP4 48 AIBN CPB 0.625 DMF 4.5 Network
PP3 66 AIBN CPB 0.625 DMF 3.0 10%
PP5 48 V-501 CDP 1 AcOH 1.0 99%
PP8 21 V-501 CDP 1 AcOH 1.0 98%

Fig. 3 Reactions for the synthesis of the ImEMA homopolymers and the ImEMASty diblock copolymers.

amphiphilic diblock copolymers of dierent compositions, are plotted in Fig. 4 against the copolymer composition. In all
ranging from 15 to 80 ImEMA mol%. cases, the pK values of the ImEMA units in the copolymers were
calculated to be around 4.5, independent of the copolymer
(Co)polymer molecular weights and compositions composition. The pK values of the diblock copolymers were
lower than that of the ImEMA monomer, which was found to be
Table 2 lists the monomer conversion (determined by 1H NMR
6.0,12,13 as expected for weak polyelectrolytes. Fig. 4 also presents
spectroscopy) and the time allowed for each polymerization
the precipitation pH of the (co)polymers. All polymers precipi-
step. Furthermore, it provides the molecular weights and
tated during titration at a pH of 3.6 or higher, with the precip-
compositions of the copolymers as determined via GPC and 1H
itation pH increasing with the increase in ImEMA content in the
NMR spectroscopy, respectively. In all cases, the ImEMA
(co)polymers. This trend can be understood considering that
conversion was 87% or higher aer 20 h of polymerization,
copolymers bearing more of the polar/hydrophilic ImEMA units
while the polymerization of Sty required longer polymerization
required a greater degree of ImEMA deprotonation (uncharg-
times.
ing) before the copolymer became water-insoluble.
As polyImEMA is insoluble in THF, GPC of the ImEMA
homopolymers and of diblocks with a low Sty content was
precluded. Hydrodynamic diameters
As shown in Table 2, the Mn value in all cases was lower (by a
Solutions of the Sty-rich diblock copolymers in chloroform were
factor of
2) than the theoretical value calculated on the basis
examined by dynamic light scattering (DLS) to determine the
of the structure of the nal copolymer determined by 1H NMR
copolymer hydrodynamic diameters and infer whether self-
spectroscopy. This underestimation of the molecular weights
assembly took place. Copolymers were studied both in their
may be due to delayed elution of the copolymers from the GPC
initial state with uncharged ImEMA units and also in the state
column arising from the presence of THF-insoluble ImEMA
with fully charged ImEMA units eected via their methylation
units. The molecular weight dispersities of the three (out of
using methyl iodide (MeI). Chloroform is a rather unpolar
four) diblock copolymers were lower than 1.3. This suggests
solvent, selective for the Sty blocks, poor solvent for the ImEMA
quasilivingness in the polymerization of Sty even with the use of
blocks, and a precipitant for the ImEMAMeI blocks. Thus, self-
a rather unusual polymerization solvent, acetic acid. The
assembly was expected to occur in this solvent, leading to the
ImEMA content in the diblock copolymers calculated from the
1 formation of micelles with ImEMA or ImEMAMeI cores and Sty
H NMR spectra of the puried and dried material spanned a
coronas. Upon methylation and charging, the ImEMA cores
broad range of values, between 15 and 80 mol% ImEMA.
were expected to become more compact, resulting in smaller
micelles. The measured hydrodynamic diameters were accord-
Eective pK values and precipitation pH ing to our expectations, and are listed in Table 3 together with
The eective pK values of the ionizable ImEMA monomer two limiting characteristic sizes for comparison. The rst
repeating units in the (co)polymers were calculated from the limiting characteristic size is the maximum possible diameter
hydrogen-ion titration curves as the pH at 50% ionization, and for spherical micelles composed of fully-stretched diblock

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Table 2 Molecular weight, composition, and monomer conversion characteristics of the polymers synthesized in this study

GPC
1
Polymerization Theoretical molecular Monomer H NMR,d
No. Polymer structure a
time (h) weightb Mp Mn conversionc ImEMA (mol%)
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1 ImEMA100 21 17 700 98
2 ImEMA100 22 15 700 87
ImEMA87-b-Sty482 70 65 800 41 700 32 400 1.27 18.6 15.3
3 ImEMA100 21.5 16 700 92.6
ImEMA93-b-Sty98 63 27 000 16 200 13 900 1.10 52.7 48.6
4 ImEMA100 21.5 16 900 94
ImEMA94-b-Sty106 63 27 900 11 800 11 100 1.10 52.8 46.9
5 ImEMA100 24 17 800 99
ImEMA99-b-Sty346 72 53 800 32 400 34 300 1.60 41.8 22.2
6 ImEMA100 24 16 900 93.7
ImEMA94-b-Sty18 120 18 900 37.9 80.4
7 ImEMA100 24 16 600 92
ImEMA92-b-Sty25 120 19 200 27.7 78.9
a
The DP of Sty was calculated from the Sty content (1H NMR) in the dried copolymer and using the calculated DP of ImEMA. b Calculated from the
DPs given in the polymer structure column. c Conversion of the last monomer polymerized. d From the 1H NMR spectrum of the dried copolymer.

Table 3 Hydrodynamic diameters of ImEMASty diblock copolymers

in chloroform

Experimental dh
Theoretically Theoretically (nm)
Polymer maximum da minimum dgb
structure (nm) (nm) CHCl3 CHCl3 + MeI

ImEMA99-b-Sty346 224.3 8.3 420 259

Dependence of the precipitation pH and the eective pK of the
Fig. 4
ImEMA monomer repeating units on the (co)polymer composition.
ImEMA87-b-Sty482 286.7 9.4 165 116
a
Calculated by multiplying the chain contour length (estimated as the
product of the overall degree of polymerization (DP) and the
contribution of one monomer repeating unit, of 0.252 nm,29 to the
contour length) by 2. b Calculated using random ight statistics
corrected for the carbon tetrahedral angle and using the PSty's
stiness factor of 2.44.29 In particular, the formula used to calculate
the root mean-square diameter of gyration was hdg2i1/2 2  (2 
2.44  DP/3)1/2  0.154, where DP is the overall degree of
polymerization and 0.154 nm is the length of one carboncarbon
bond.29

copolymers (2  contour length), whereas the other limiting

characteristic size is the diameter of gyration of individual
diblock copolymers (unimers) in a random coil conguration.29
The table presents information only on the two Sty-rich copol-
ymers, as the chloroform solutions of the other copolymers
could not be ltered for sample preparation for DLS.
The results suggested that both copolymers aggregated in
chloroform because their experimentally measured hydrody-
namic diameters were much larger than the corresponding
unimer diameters of gyration (theoretically minimum size) and
close to the corresponding spherical micelle diameters (theo-
retically maximum size). Iodomethylation resulted in signi-
cant (
40%) micelle shrinkage due to the quaternization of the
core-forming ImEMA block leading to its enhanced incompat-
ibility with the solvent. Note that the diblock copolymer
ImEMA99-b-Sty346 formed larger micelles due to its higher
content in the ImEMA core block (22 mol%) compared to that of
ImEMA87-b-Sty482 (15 mol% ImEMA). It is noteworthy, however,
that all size distributions were multimodal, with lower-intensity
populations appearing at 2030 nm, probably corresponding to
unimers, and also at 450650 nm, corresponding to micellar
clusters.
Birefringence in the bulk and in water
The self-assembly in water and in the bulk (dried state) of all the
amphiphilic diblock copolymers was qualitatively investigated
by polarized light microscopy (PLM). Fig. 5 shows the PLM
images of all amphiphilic diblock copolymers plus that for the
ImEMA homopolymer, in the absence and presence of water.
The pictures are arranged in order of increasing (co)polymer
hydrophilicity. Whereas no birefringence was observed for any
of the dried samples, all water-swollen copolymer samples
exhibited birefringence, manifesting phase separation into
anisotropic nanophases displaying dierent refractive indices.
Additionally, the color intensity decreased as the ImEMA
content increased, with the ImEMA homopolymer displaying no

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Fig. 5 Polarized light microscopy images of the ImEMA-containing (co)polymers both in the dried and the water-swollen states
(100 magnication, picture length: 312 mm).
Fig. 6 TGA thermograms of the ImEMA100 and Sty100 homopolymers,
and the ImEMA99-b-Sty346 diblock copolymer.
birefringence at all. This indicated that shorter hydrophobic
blocks yielded nanophases of lower anisotropy and eventually
structures with no nanophase separation at all, as was expected
for the ImEMA homopolymer. In the images, the coloration in
the samples clearly came from the bulk of the ground particles
and not from reections from surface planes cut in irregular
ways.
Thermolysis and hydrolysis of the ImEMA homopolymer
The thermal decomposition of the ImEMA units was studied by
TGA and DSC. The TGA thermograms of ImEMA100, Sty100 and
ImEMA99-b-Sty346 are displayed in Fig. 6. While the TGA ther-
mogram of the Sty homopolymer presented a single-step weight
loss at
400  C, those of the ImEMA-containing polymers pre-
sented two steps of weight loss. The rst one took place at

270  C where the ImEMA units lost the mass percentage cor-
responding exactly to the 2-(1-imidazolyl)ethyl side-groups
(observe the good agreement between the theoretically expected
remaining mass percentage and the end of the rst part of the
thermogram), while the second stage of weight loss took place
at about 400  C corresponding to main-chain decomposition.
The 2-(1-imidazolyl)ethyl group is more stable compared to
the 2-(pyridin-2-yl)ethyl group, with the latter group being
removed at a much lower temperature of 200  C.30 The greater
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Polymer Chemistry
lability of the 2-(pyridin-2-yl)ethyl group is due to the electron-
withdrawing property of the nitrogen atom at its present posi-
tion in the pyridine ring, rendering the protons of the methy-
lene group at the a-position from the pyridine ring more acidic.
In contrast, in the case of the imidazole ring, there are two
nitrogen atoms: one acting as a pyrrole nitrogen, and the other
being an electron-withdrawing one just as the pyridine
nitrogen. In the 2-(1-imidazolyl)ethyl group, the substituent is
on the electron-withdrawing nitrogen and, therefore, the
imidazole ring becomes more electron-rich and the protons at
the a-position are not acidic.
The ImEMA homopolymer was also characterized by dier-
ential scanning calorimetry (DSC). Fig. 7 displays DSC ther-
mograms of ImEMA100 for two temperature ranges. Fig. 7(a)
covers the temperature range between 40 and 350  C, whereas
Fig. 7(b) covers that between 40 and 220  C. In each case, two
heating cycles were recorded, as well as the intermediate cool-
ing step. Fig. 7(a) exhibited two endotherms in the rst heating
cycle, one at a lower temperature range,
50100  C, and the
other at a higher range,
270330  C. Neither of these endo-
therms was reproduced during the second heating cycle. We
suggest that the lower temperature endotherm was due to
evaporation of solvent, probably water, while the higher
temperature one was due to the irreversible chemical reaction
leading to the cleavage of the ImEMA side group, and resulting
in the formation of MAA units. This latter temperature
(
290  C) is close to the one determined by TGA (
270  C), also
assigned to side-group cleavage.
The DSC runs in Fig. 7(b) were kept below the temperature of
cleavage of the ImEMA units, so that aer the solvent removal in
the rst heating run, the second heating run reveals the glass
transition temperature of the polymer. Although the solvent
peak was indeed absent in the second heating run, no thermal
transition due to the polymer was clearly presented. The pres-
ence of a crystalline impurity in the system is the probable cause
of the slight melting endotherm at
7080  C in the heating
runs in both Fig. 7(a) and (b), which also appears as a slight
crystallization exotherm in the cooling run in Fig. 7(a).
Given the thermal lability of the ImEMA units revealed from
the TGA and DSC measurements, we decided to investigate the
thermal decomposition of ImEMA100 by 1H NMR spectroscopy
at a lower (than
280  C) temperature and for longer times.
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Polymer Chemistry
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Fig. 7 DSC thermograms of the ImEMA homopolymer during two
heating runs and the intermediate cooling step. Temperature ranges:
(a) 40 to 350  C, and (b) 40 to 220  C.
Thus, several portions of an ImEMA100 homopolymer were
placed in a vacuum oven maintained at 110  C, and samples
were withdrawn aer 2, 3 and 5 h, and 3 days of thermolysis,
and analyzed by 1H NMR spectroscopy in d6-DMSO. The recor-
ded spectra are displayed in Fig. 8, which show that the main
thermolysis products were ImEOH and poly(methacrylic acid)
(polyMAA), resulting from the cleavage of the side-group of the
ImEMA units. NVIm was also produced during thermolysis, but
this was probably formed from the dehydration of ImEOH (and
not directly from ImEMA), as NVIm was always observed
together with ImEOH, with the 1H NMR signals from NVIm
always being much weaker than those from ImEOH. Similar
results were also observed by Ivan and coworkers3 who studied
the thermal decomposition of linear homopolymers of NVIm.
From the 1H NMR spectra, data were extracted to follow the
kinetics of the thermolysis and also to determine the nal yield.
The conversion of the thermolysis quickly reached
70% within
the rst 2 h, and the reaction did not proceed further, even aer
72 h. The conversion of the themolysis was calculated by
ratioing the signal from the two ethyl protons i (3.98 ppm) of
the produced ImEOH to the sum of those protons and the four
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1
Fig. 8 H NMR spectra in d6-DMSO of samples obtained during the
thermolysis of ImEMA100 at 110  C.
corresponding ethyl protons c and d in polyImEMA (4.23
ppm). When the thermolysis was performed at a higher
temperature (200  C), the full conversion of polyImEMA to
polyMAA was achieved within 4 h.
The removal of the side-groups of the ImEMA homopolymer
was also attempted by alkaline hydrolysis (concentration of
NaOD 0.67 M) in a mixture of d4-methanol and d6-DMSO at
room temperature. The reaction was slow and required four
weeks to reach 50% conversion. In this case, the hydrolysis
products were polyMAA and ImEOH rather than NVIm, as
dehydration of ImEOH was apparently not favored under these
conditions.
Finally, the stability of the ImEMA homopolymer was
examined under acidic conditions too, using DCl at a concen-
tration of 0.67 M in d6-DMSO at room temperature. The
homopolymer remained stable under these conditions even
aer 2 days. The only noteworthy observation from the 1H NMR
spectra was the downeld shi of the signals from the aromatic
protons due to the protonation of the imidazole ring.
Conclusions
RAFT polymerization was successfully employed for the
synthesis of ImEMASty amphiphilic diblock copolymers of
dierent compositions. The copolymer molecular weights
ranged from 11 000 to 34 000 g mol1, while the ImEMA content
varied from 15 to 80 mol%. The ImEMA units are stable in the
(co)polymers up to 250  C, above which the ImEMA side-groups
are cleaved. At room temperature, the ImEMA units are
This journal is The Royal Society of Chemistry 2014

Paper
hydrolytically stable under acidic conditions, but they undergo
slow alkaline hydrolysis. Microphase separation of the diblock
copolymers was also studied by DLS and polarized light
microscopy. DLS indicated spherical micelle formation in
chloroform. Polarized light microscopy indicated microphase
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separation of the diblock copolymers in water into anisotropic
structures, whose birefringence increased with the copolymer
hydrophobic content.
Acknowledgements
We acknowledge the European Regional Development Fund
and the Republic of Cyprus for cofunding this work through
Cyprus Research Promotion Foundation in the form of a
DIDAKTOR 20092010 Doctoral Research Fellowship (project
code: DIDAKTOR/0311/80) to M. R.-K. The same organizations
are also thanked for cofunding an infrastructure grant, NEKYP/
0308/02, which allowed the purchase of the 500 MHz NMR
spectrometer used in this work. Finally, we thank our colleagues
at the University of Cyprus, Professor E. Leontidis for providing
access to his polarized light microscope, and Prof. P. A. Kou-
tentis for providing access to his TGA and DSC instruments.
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