Macromolecular

Rapid Communications Communication

Individually Addressable Thermo- and Redox-

Responsive Block Copolymers by Combining
Anionic Polymerization and RAFT Protocols

Bernhard V. K. J. Schmidt, Johannes Elbert, Christopher Barner-Kowollik,*

Markus Gallei*

A novel diblock copolymer consisting of poly(vinylferrocene) (PVFc) and poly(N,N-diethyl-

acrylamide) (PDEA) is synthesized via a combination of anionic and RAFT polymerization.
The use of a novel route to hydroxyl-end-functionalized
metallopolymers in anionic polymerization and subsequent
esterification with a RAFT agent leads to a PVFc macro-CTA
( Mn = 3800 g mol−1; Ð = 1.17). RAFT polymerization with DEA
affords block copolymers as evidenced by 1H NMR spectros-
copy as well as size exclusion chromatography (6400 ≤ Mn ≤
33700 g mol−1; 1.31 ≤ Ð 1.28). Self-assembly of the amphiph-
ilic block copolymers in aqueous solution leads to micelles as
shown via TEM. Importantly, the distinct thermo-responsive
and redox-responsive character of the blocks is probed via
dynamic light scattering and found to be individually and
repeatedly addressable.

1. Introduction range, e.g., from fields of nanolithography, drug delivery

Amphiphilic block copolymers have attracted significant
interest owing to their ability to self-organize in selective
solvents forming micelles or vesicles based on the solu-
bility of their hydrophobic and hydrophilic segments.[1–4]
The applications of block copolymers are manifold and
Dr. B. V. K. J. Schmidt, Prof. C. Barner-Kowollik
Preparative Macromolecular Chemistry, Institut für Technische
Chemie und Polymerchemie, Karlsruhe Institute of Technology
(KIT), Engesserstraße 18, 76131 Karlsruhe, Germany and Institut
für Biologische Grenzflächen, Karlsruhe Institute of Technology
(KIT), Hermann-von-Helmholtz-Platz 1, 76344 , Eggenstein-
Leopoldshafen, Germany
E-mail: christopher.barner-kowollik@kit.edu
J. Elbert, Dr. M. Gallei
Ernst-Berl Institut für Technische und Makromolekulare
Chemie, Technische Universität Darmstadt, Alarich-Weiss-
Straße 4, 64287, Darmstadt, Germany
E-mail: m.gallei@mc.tu-darmstadt.de
to separation technologies.[5–12] Furthermore, so-called
stimuli-responsive polymers, i.e., polymers, which are able
to change their conformation, solubility, or even break or
form covalent bonds caused by an external trigger, have
attracted significant attention in the last decade.[13–19] For
example, Smith et al. reported the self-assembly and dual
responsive behavior of “schizophrenic” diblock copolymer
micelles. The multiple nanostructures obtained in water
were not only dictated by the block length of the soluble
segments but also by varying the pH value or tempera-
ture.[20] The thermo- and photoresponsiveness of poly-
meric micelles in water has recently been applied for the
efficient release of an encapsulated dye.[21] Although
the vast majority of reports about external triggers for
stimuli-responsive materials focus on changing the tem-
perature, light, and/or the pH value, also other stimuli
are of growing interest.[14,22] Fewer examples are reported
and well investigated for redox-responsive polymers
and block copolymers.[23–25] In the last decade, ferro-
cene-containing polymers were especially of interest to

Macromol. Rapid Commun. 2014, 35, 708−714

708 © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com DOI: 10.1002/marc.201300870

Individually Addressable Thermo- and Redox-Responsive Block Copolymers . . .
scientists owing to the excellent combination of redox,
mechanical, semi-conductive, photo-physical, and opto-
electronic properties.[26–28] For example, such ferrocene-
containing polymers have been utilized as self-healing
materials,[29] in composite colloidal crystal films,[30] for a
redox-responsive release from patchy nanocapsules,[31] for
modulating the activity of catalysts,[32] or for ion-selective
membrane-gating through nanopores.[33] The fascinating
solution self-assembly of polyferrocenylsilane-based (PFS)
block copolymers has been studied by Manners and co-
workers.[34–37] Besides the PFS systems carrying the fer-
rocene moiety as part of the polymer backbone, polymers
carrying the ferrocene unit laterally have been studied in
selective solvents, e.g., poly(vinylferrocene) (PVFc).[38–40]
Both the variety of applications of block copolymers
in bulk and in selective solvents are based on controlling
the self-assembly, which again necessitates the precise
synthesis of the block copolymer architectures in terms
of block length and constitution. This basic prerequisite
for the preparation of highly ordered micro domains can
be fulfilled by using controlled or living polymerization
methodologies.[3] Combinations of different poly-
merization techniques with RAFT polymerization have
been in the focus of polymer chemists and several meth-
odologies have been developed in the past few years.
Thus, the range of possible block copolymer combina-
tions could be broadened even further than with RAFT
polymerization alone. Examples include the cationic
ring opening polymerization of 2-oxazolines and poly-
thiourethanes,[41,42] the cationic polymerization of vinyl
ethers,[43] and ring-opening polymerization of epoxides[44]
or lactones.[45,46] In the area of anionic polymerization, a
frequently utilized route is the synthesis of a hydroxy-
end-functionalized polymer and subsequent esterifica-
tion with an acid-bearing chain transfer agent (CTA)[47] to
gain access to new materials. Recently, a one-pot transfor-
mation of living anionic chain ends into a CTA moiety has
been described.[48]
To combine anionically synthesized PVFc blocks with
RAFT, we chose to utilize an esterification route. There-
fore, a novel methodology for hydroxyl endcapping
was used, which was analyzed via matrix-assisted laser
desorption ionization-time of flight mass spectrom-
etry (MALDI-ToF MS) and NMR spectroscopy, and sub-
sequently a CTA was esterified to gain access to a PVFc
macro-CTA. Herein, we describe the combination of
anionic-polymerization-derived redox-responsive PVFc
blocks with RAFT-polymerization-derived thermo-respon-
sive poly(N,N-diethylacrylamide) (PDEA) blocks, which
were characterized via NMR and SEC. Micelle formation
was followed by using transmission electron micros-
copy (TEM). The multi stimuli-responsive character of the
obtained block copolymers was investigated via dynamic
light scattering (DLS).
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2. Results and Discussion
Poly(vinylferrocene) (PVFc) was prepared via anionic poly-
merization leading to narrowly distributed molar masses
following previously published protocols.[49] The active
PVFc macro-anions were treated with N,N-dimethyl-
formamide (DMF) according to Scheme 1. After precipi-
tation of the corresponding metallo-polymer bearing a
telechelic aldehyde functionality (PVFc-CHO 5) with Mn
of 2400 g mol−1 and Ð of 1.17 was isolated. The aldehyde
functionality was formed after conversion of the unstable
hydroxyl dimethyl amino intermediate during the work-up
procedure. 1H NMR spectroscopy only gives limited infor-
mation for the successful end functionalization reaction as
in general broad and unstructured absorptions caused by
PVFc were observed (Figure 1b). On the other hand, matrix-
assisted laser desorption ionization-time of flight mass
spectrometry (MALDI-ToF MS) evidences the successful
end functionalization with an efficiency of 92% (Figure 1a
and Table S1, Supporting Information). The distances of the
mass series are 212 g mol−1, which correspond to the vinyl-
ferrocene unit. The disappearance of the corresponding
aldehyde signals in the 1H NMR spectrum (Figure S2, Sup-
porting Information) underpins the successful reduction
of PVFc-CHO 3 with LiAlH4 to yield PVFc-OH 4 (Figure S3,
Supporting Information). The metallo-polymer was con-
verted to the PVFc-CTA 5 by reacting with acid containing
RAFT agent 2-(dodecylthiocarbonothioylthio)propionic
acid (DoPAT) via EDC-mediated esterification. 1H NMR
shows the incorporation of the RAFT agent (Figure 1b), e.g.,
the resonances of the methyl group of the dodecyl chain
at 0.8 ppm that resembles in the macro-RAFT agent spec-
trum yet slightly broadened. Unfortunately, it was not pos-
sible to obtain a MALDI-ToF spectrum for PVFc-CTA 5 due
to fragmentation of the DoPAT group during the measure-
ment, as the RAFT end group is already UV sensitive.
Block copolymers of PVFc and PDEA were formed in a
RAFT polymerization employing PVFc-CTA as macro-RAFT
agent (Scheme 1). The polymerization was conducted
in 1,4-dioxane at 60 °C with AIBN as an initiator. A ratio
of CTA/AIBN of 5:1 was employed in order to obtain an
efficient RAFT process and thus a well-controlled poly-
merization. To prove the reversible-deactivation poly-
merization character, the polymerization kinetics were
studied (Figure S4, Supporting Information). In addition,
a shift in the SEC traces is observed with conversion with
only minor amounts of residual PVFc precursor (Figure 1c,
Figure S5, Supporting Information). The content of residual
PVFc-CTA precursor that did not initiate the poly-
merization of DEA was determined to be close to 7 wt%
(RI signal) and 9 wt% (UV signal) by Gaussian approxi-
mation based on the corresponding SEC traces. Block
copolymers with Mn ranging from 6400 to 33 700 g mol−1
were achieved in reaction times of up to 5 h with Ð
709
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Rapid Communications B. V. K. J. Schmidt et al.

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Scheme 1. Synthesis of polyvinylferrocene-CTA 5 (PVFc-CTA) by end functionalization of living PVFc macro-anions with DMF followed by
reduction of the PVFc-aldehyde PVFc-CHO 3. After esterification with DoPAT, PVFc-CTA 5 can be used for the polymerization of DEA after
initiation with AIBN.

decreasing from 1.31 to 1.28 during the polymerization overlapping with the forming block copolymers in the SEC
process (Table 1). While a Ð below 1.4 is obtained at ele- trace. A high Ð of 2.18 is estimated due to the presence of
vated conversions, at a conversion of 22% a second dis- residual homopolymer. In the other cases, minor tailing
tribution corresponding to non-functionalized PVFc is towards lower molecular weights is observed resulting in

Figure 1. a) Stacked MALDI-ToF mass spectra of the PVFc precursor sample, which was terminated with methanol (PVFc-H) and the cor-
responding mass spectrum after functionalization of the living PVFc carbanions with DMF and work-up procedure, b) 1H NMR spectra of
DoPAT (1), PVFc-OH (2), PVFc-CTA (3) and PVFc18-b-PDEA198(4) and c) molecular weight distribution of PVFc-CTA 5 (straight line) and PVFc18-
b-PDEA198 (dashed line).

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Table 1. Results of the RAFT chain extension of PVFc-CTA in From the TEM images, it can be concluded that remark-
1,4-dioxane at 60 °C with a ratio of PVFc-CTA/DEA/AIBN of able uniform micelles were obtained similar to previously
1/334.5/0.2.
reported PVFc-based block copolymers.[38,39]
Time Conversiona) M n ,theo M n,SECb) Ðb) The main objective of the current work—besides the
[min] [%] [g mol−1] [g mol−1 ] development of a powerful synthetic strategy by com-
0 0 – 2400 1.17 bining living anionic and RAFT polymerization strate-
120 22 11 800 6400 2.18c) gies—was to characterize the thermo- and redox-respon-
siveness of the corresponding block segments. To ensure
180 33 16 400 19 300 1.28
that both stimuli – temperature and redox-responsive-
240 62 28 800 27 600 1.29 ness—can be addressed almost independently of each
300 76 34 700 33 700 1.31 other, the reduced ferrocene-containing micelles as well as
PVFc-H a) 1400 1.14 the oxidized ferrocene-containing micelles were brought
b) repeatedly above or below the LCST of PDEA. Therefore,
PVFc-H 3900 1.13
the micelles formed in water were heated above the cloud
a)
Determined via SEC in THF at 35 °C with poly(styrene) stand- point (Tc) of PDEA (Figure 3). Optical inspection already
ards; b)Determined via SEC-MALLS in THF at 35 °C, dn/dc = 0.168; evidences that a collapse of the corona chains occurs at
c)
Determined for the bimodal molecular weight distribution elevated temperatures. To determine the Tc of PDEA as part
inclusively the residual PVFc-CTA macro-initiator.
of the block copolymer system, additional DLS measure-
ments were carried out (Figure S6, Supporting Informa-
the increase of Ð from 1.17 for PVFc-CTA to 1.31 for PVFc- tion) determining the Tc to be 30 °C. The thermo-respon-
b-DEA with the highest degree of polymerization. siveness is fully reversible many times. To investigate the
The formation of block copolymers was further inves- redox-responsiveness of the ferrocene-containing block
tigated via 1H NMR, where signals corresponding to both segment, the micelles were treated with iron(III) chloride
blocks are evident (Figure 1b), e.g., the ferrocene signals as an oxidizing reagent. Immediately, the color of the solu-
between 3.5 and 4.5 ppm and the methylene signals from tion changes from slightly amber to deep green due to the
the DEA side-chain between 2.7 and 3.5 ppm. oxidation of the ferrocene moieties. Furthermore, this pro-
To evidence the amphiphilic character of the novel cess is accompanied by breaking the micellar structures,
metallo-block copolymers obtained, a sample of PVFc18- which is also observed via DLS measurements (Figure S6,
b-PDEA198 was dissolved in a small amount of THF and Supporting Information). Again, this process is fully revers-
treated with a large excess of water, leading to the forma- ible—as confirmed via DLS as well—for at least five times
tion of micelles. It is worthy to note that all herein inves- by reducing the ferrocenium moieties with ascorbic acid.
tigated polymers exhibit an excellent dispersibility in To confirm the thermo-responsiveness of the oxidized
polar solvents such as water or DMF. To gain insight into metallo-polymer micelles in water, the solution was again
the formation of micellar aggregates, TEM images of the heated above the Tc of PDEA. This led to a collapse of PDEA
micellar solutions were recorded. Therefore, the sample and formation of micelles featuring a PDEA core and a
was drop-casted on a carbon-coated copper grid followed PVFc+-containing corona. Again, DLS measurements were
by drying in vacuo prior to the measurements (Figure 2). carried out to determine the exact Tc. This time, the Tc

Figure 2. TEM images of PVFc18-b-PDEA198 micelles formed in water. The micelles were deposited on a carbon-coated copper grid followed
by drying at ambient temperature. Scale bars correspond to 1000 nm (left) and 250 nm (right).

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Figure 3. Scheme and images (black: DEA, orange: PVFc, green: PVFc+) of the four dif-
ferent states of PVFc-b-DEA in water as a function of temperature and oxidation state.
was slightly higher (32 °C) compared to the reduced PVFc-
containing micelles. These results demonstrate that both
stimuli, temperature and redox reagents, can individually
address the conformational changes of the corresponding
block segments.
3. Conclusion
In the current study, we have presented an efficient pro-
tocol for the hydroxy end functionalization in anionic
polymerization, which is utilized to perform a mechanistic
switch to RAFT polymerization. Such an approach leads
to the formation of a novel PVFc-b-PDEA block copolymer
that shows dual-stimuli-responsive character. It has been
proved that the respective thermo- and redox-responsive
character of the blocks could be addressed individually
many times, which gives rise to future applications in
aqueous systems, such as drug delivery.
4. Experimental Section
4.1. Synthesis of PVFc-CHO and PVFc-OH
In an ampoule equipped with a stirring bar, VFc (1.13 g,
5.3 mmol) is dissolved in neat THF (25 mL). The solution is cooled
to −15 °C followed by the addition of n-BuLi in hexane (0.202 mL,
Macromol. Rapid Commun. 2014, 35, 708−714
712 © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
B. V. K. J. Schmidt et al.
1.6 M, 0.32 mmol). After stirring the solution
for 16 h at −15 °C inside the Coldwell appa-
ratus, an aliquot is taken from the ampoule
and treated with 0.1 mL MeOH for SEC, SEC-
MALLS, and MALDI-ToF MS measurements.
The aliquot is poured into a tenfold excess of
methanol for precipitation of the PVFc pre-
cursor. The polymer is filtered, washed with
methanol and dried in vacuo. To the solu-
tion with living PVFc macro-anions, dry DMF
(0.123 mL, 1.6 mmol, 5 eq. with respect to
the living PVFc chain ends) is added during
vigorous stirring and the mixture is allowed
to warm up to room temperature. After stir-
ring for another 10 h at RT, the solution is
poured into methanol (250 mL). The pre-
cipitated polymer is collected by filtration,
washed with methanol, and dried in vacuo.
Yield: 1.21 g (quantitative).1H NMR(CDCl3):
δ = 0.80–2.70 (alkyl), 3.65–4.55 (cyclopenta-
diene), 9.55–9.98 (CHO) ppm.
For reduction of PVFc-CHO, the polymer
(1.21 g) is dissolved in 5 mL neat THF and
the solution is added dropwise to a slurry of
lithium aluminum hydride (LAH, 12 mg, 1 eq.
in 10 mL neat THF) at room temperature. The
solution is stirred for 24 h and poured onto
ice. The polymer is filtered, washed with
methanol, and dried in vacuo. Yield: 1.19 g
(quantitative).
4.2. Synthesis of PVFc-CTA
In a dried 100-mL Schlenk flask, DoPAT (585 mg, 1.67 mmol,
5.0 eq.), PVFc18-OH (1.00 g, 0.33 mmol, 1.0 eq.), and DMAP
(8.0 mg, 0.07 mmol, 0.2 eq.) were dissolved in a mixture of anhy-
drous DCM (20 mL) and anhydrous THF (10 mL) under argon. At
0 °C, EDC*HCl (318 mg, 1.66 mmol, 5.0 eq.) was added and the
mixture stirred for 2 d at ambient temperature. Subsequently,
the mixture was filtered and the polymers precipitated in a ten-
fold excess of cold methanol. The precipitate was collected via
filtration, dissolved in a small amount of THF and precipitated
again in a tenfold excess of cold methanol. Finally, the product
PVFc18-CTA (528 mg, 53%) was collected and dried under
vacuum.
4.3. Synthesis of PVFc18-b-PDEA198
PVFc-CTA (50.0 mg, 0.02 mmol, 1.0 eq.), DEA (850.0 mg,
6.69 mmol, 334.5 eq.), AIBN (0.6 mg, 0.004 mmol, 0.2 eq.), and
1,4-dioxane (6.0 mL) were mixed. The mixture was separated
into five Schlenk-tubes and stirring bars were added. After
three freeze-pump-thaw cycles, the tubes were backfilled with
argon, sealed, and placed in an oil bath at 60 °C. After prede-
termined times, the tubes were removed from the oil-bath
and subsequently cooled with liquid nitrogen to stop the
reaction. A NMR-sample was withdrawn for the determina-
tion of conversion and CDCl3 was added (see Characterization
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Individually Addressable Thermo- and Redox-Responsive Block Copolymers . . .
Methods for details of the calculation). The residue was dia-
lyzed against deionized water with a SpectraPor3 membrane
(MWCO = 1000 Da) for 3 d at ambient temperature. The solvent
was removed in vacuo to yield the polymers as orange solids
(Table 1 for analytical details).
4.4. Preparation of Micelles for Optical Characterization
and Investigation of the Dually Stimuli Responsiveness
PVFc18-b-PDEA198 (5 mg, 1.48 μmol) was dissolved in THF (0.1 mL)
and added dropwise to an excess of deionized water (1.5 mL). A
slightly turbid orange suspension was obtained that was utilized
to probe the different stimuli and take pictures of the macro-
scopic effect.
Samples for DLS: To 300 μL of a solution of PVFC18-b-PDEA198 in
THF (10 mg mL−1) 2.7 mL water is added dropwise and the solu-
tion is stirred for 30 min at room temperature.
4.5. Oxidation and Reduction of the Block Copolymer
Micelles
To oxidize the ferrocene moieties, 500 μL of a 1 M solution of FeCl3
in water is added to the micellar solution. For reducing the ferro-
cenium units, 1 mL of a 1 M solution of L-ascorbic acid in water is
added to the micellar solution.
Supporting Information
Supporting Information is available from the Wiley Online
Library or from the author.
Acknowledgements: The authors thank Karsten Rode and
Julia Beer for performing the MALDI-ToF measurements.
C.B.-K. acknowledges continued funding from the Karlsruhe
Institute of Technology (KIT) in the context of the Helmholtz
research programs BioInterfaces and STN, the German Research
Council (DFG) as well as the ministry of science and arts of
the state of Baden-Württemberg. M.G. and J.E. would like to
thank the Landesoffensive zur Entwicklung Wissenschaftlich-
ökonomischer Exzellenz (LOEWE “Soft Control”) for on-going
financial support.
Received: November 25, 2013; Revised: December 15, 2013; Pub-
lished online: January 27, 2014; DOI: 10.1002/marc.201300870
Keywords: anionic polymerization; ferrocene; RAFT poly-
merization; redox-responsive; thermo-responsive
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