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

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

scientists owing to the excellent combination of redox, 2. Results and Discussion

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

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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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 Macromolecular
Individually Addressable Thermo- and Redox-Responsive Block Copolymers . . . Rapid Communications
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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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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
Figure 3. Scheme and images (black: DEA, orange: PVFc, green: PVFc+) of the four dif- solution is stirred for 24 h and poured onto
ferent states of PVFc-b-DEA in water as a function of temperature and oxidation state. ice. The polymer is filtered, washed with
methanol, and dried in vacuo. Yield: 1.19 g
was slightly higher (32 °C) compared to the reduced PVFc- (quantitative).
containing micelles. These results demonstrate that both
stimuli, temperature and redox reagents, can individually
4.2. Synthesis of PVFc-CTA
address the conformational changes of the corresponding
block segments. 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-
3. Conclusion 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,
In the current study, we have presented an efficient pro-
the mixture was filtered and the polymers precipitated in a ten-
tocol for the hydroxy end functionalization in anionic
fold excess of cold methanol. The precipitate was collected via
polymerization, which is utilized to perform a mechanistic filtration, dissolved in a small amount of THF and precipitated
switch to RAFT polymerization. Such an approach leads again in a tenfold excess of cold methanol. Finally, the product
to the formation of a novel PVFc-b-PDEA block copolymer PVFc18-CTA (528 mg, 53%) was collected and dried under
that shows dual-stimuli-responsive character. It has been vacuum.
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 4.3. Synthesis of PVFc18-b-PDEA198
aqueous systems, such as drug delivery. 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
4. Experimental Section 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-
4.1. Synthesis of PVFc-CHO and PVFc-OH
termined times, the tubes were removed from the oil-bath
In an ampoule equipped with a stirring bar, VFc (1.13 g, and subsequently cooled with liquid nitrogen to stop the
5.3 mmol) is dissolved in neat THF (25 mL). The solution is cooled reaction. A NMR-sample was withdrawn for the determina-
to −15 °C followed by the addition of n-BuLi in hexane (0.202 mL, tion of conversion and CDCl3 was added (see Characterization

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Individually Addressable Thermo- and Redox-Responsive Block Copolymers . . . Rapid Communications
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