Article

pubs.acs.org/Macromolecules

Sulfur-Functionalized Graphenes as Macro-Chain-Transfer and RAFT

Agents for Producing Graphene Polymer Brushes and Polystyrene
Nanocomposites
Fabian Beckert, Christian Friedrich, Ralf Thomann, and Rolf Mulhaupt*
Freiburg Materials Research Center, FMF and Institute for Macromolecular Chemistry of the University of Freiburg,
Stefan-Meier-Str. 31, D-79104 Freiburg, Germany
ABSTRACT: Novel families of polystyrene carbon nanocomposites and
graphene brushes were prepared by means of free radical styrene grafting
using sulfur-functionalized graphene (S-FG) as macro-chain-transfer
agent. Two strategies were examined for growing polystyrene chains
onto graphite oxide (GO), stearylamine-modied GO (Stearyl-GO), and
thermally reduced GO (TRGO): (i) chain transfer with novel thiolfunctionalized graphenes and (ii) RAFT-mediated polymerization using
dithiourethane-, dithioester- and dithiocarbonate-functionalized graphenes. Novel thiol-functionalized graphenes were obtained from FG either
by esterication with 3-mercaptopropionic acid or by reaction with
propylene sulde. The styrene graft polymerization was initiated either with AIBN at 65 C or by thermal styrene self-initiation at
130 C. The graphene content, varying between 0 and 5.2 wt %, was determined by means of thermogravimetric analysis (TGA).
Upon hydrolytic cleavage of the dithiocarbonate linker, the stability of the S-FG dispersion in polystyrene was lost, and the
nonbonded S-FG was separated quantitatively from polystyrene by solvent extraction. During melt processing the graphene
brushes self-assembled to produce nanoribbons and skeleton-like carbon superstructures, as determined by means of
transmission electron microscopy (TEM). Both grafting eectiveness and superstructure formation were monitored by means of
melt rheology.

INTRODUCTION

research objective to attach polymers to graphenes by means of

covalent bond formation.
Several grafting-from and grafting-o routes have been
explored using either graphite or functionalized graphenes as
intermediates for the preparation of graphene brushes and
sheet-coil carbon polymers.14 Although direct grafting of
graphite is very attractive and cost-eective, few examples have
been successful because grafting must be accompanied by
intercalation and eective exfoliation of single graphenes from
graphite during the grafting process. The use of alkali metal
graphite intercalates as macroinitiators for anionic styrene
grafting,15 mechanochemical production of polystyrene graphene nanocomposites,16,17 and electrochemical graphite
activation in ionic liquids18 have been reported. Most
approaches employ functionalized graphenes (FG) which are
easy to disperse in various organic media. Moreover, the
functional groups of FG are readily modied to produce
macroinitiators, macromonomers, and macro-chain-transfer
agents. The key intermediate is graphite oxide (GO), derived
from graphite which is intercalated in sulfuric acid and oxidized
with strong oxidizing agents such as potassium permanganate
or sodium chlorate.1921 Upon chemical or thermal reduction,
GO is converted into FG containing hydroxyl, phenoxy,

Graphenes represent one-carbon-atom thick and micrometerwide two-dimensional carbon macromolecules consisting of a
honeycomb-like hexagonal array of sp2-bonded carbon
atoms.1,2 They exhibit extraordinary property combinations
such as very high stiness and strength, high electron mobility
at room temperature, tunable band gap, high thermal
conductivity, optical transparency, excellent thermal and
environmental stability, high abrasion resistance, and very
eective absorption of UV and IR radiation.3,4 A wide range of
graphene applications are currently being envisioned, including
advanced functional materials such as transparent electrodes as
ITO substitute,5 printable electronics,6 sensors,7 membranes,8
ultrathin carbon lms,9 catalyst supports,10 coatings,11 and
polymeric graphene nanocomposites for advanced engineering
plastics.12,13 The incorporation of small amounts of graphenes
into polymers can aord substantial matrix reinforcement,
improved damage tolerance, electrical and thermal conductivity,
electromagnetic shielding, corrosion protection, abrasion
resistance, ame retardancy, and even barrier resistance against
permeation of gases and uids. It is well-known that the
nanocomposite properties strongly depend upon eective
graphene dispersion, good interfacial adhesion, and supramolecular graphene self-assembly producing skeleton-like
carbon superstructures. In order to control both dispersion
and self-assembly during melt compounding, it is an important
2012 American Chemical Society

Received: July 4, 2012

Revised: August 13, 2012
Published: August 30, 2012
7083

dx.doi.org/10.1021/ma301379z | Macromolecules 2012, 45, 70837090

Macromolecules

carboxyl, and epoxy groups. During the thermal reduction, the

FG oxygen content is governed by the reduction temperature.22,23 The strongly hydrophilic GO, which is dicult to
disperse in styrene, is rendered hydrophobic when hydroxyl
groups are converted with phenyl isocyanate into organophilic
phenylurethane groups.24 In an alternative GO modication,
the GO epoxy groups are reacted with stearylamine to form
organophilic and easy-to-disperse amphiphilic stearylaminemodied GO (Stearyl-GO), which is partially reduced during
this amine addition reaction.25 Ruo and co-workers have
prepared novel GO-based macroinitiators for initiating the free
radical graft polymerization on the FG. The hydroxyl groups of
GO are esteried with -bromoisobutyryl bromide to produce
graphene macroinitiators for styrene grafting via atom transfer
radical polymerization (ATRP).26,27 Novel acrylic FG macromonomers are obtained when GO hydroxyl groups are
esteried with methacryloyl chloride.28 As a function of the
FG acrylate functionality, the FG acrylate content and the
acrylate conversion during polymerization, grafting, and crosslinking could take place simultaneously.
Chain-transfer agents containing dithioester, dithiourethane,
and di- or trithiocarbonate moieties are used extensively in
reversible additionfragmentation chain transfer (RAFT) and
controlled radical graft polymerization for tailoring segmented
of polymers and core/shell particles.29 Most FG-based macrochain-transfer agents have been derived from GO. Sanderson et
al. reported the esterication of the GO hydroxyl groups with
dodecyl isobutyric acid trithiocarbonate. Incorporation of the ndodecyl chains renders the GO chain-transfer agent hydrophilic, thus improving compatibility with organic solvents and
monomers commonly used in controlled radical polymerization. This GO-RAFT system enables the styrene miniemulsion polymerization producing coreshell particles.30
Another GO-RAFT macro-chain-transfer agents has been
designed by Kang et al. for growing poly(N-vinylcarbazole)
onto GO sheets.31 Han and Qi produced GO-RAFT systems in
a multistep synthesis via esterication of the GO carboxylic acid
groups to dithioesters. The resulting GO-RAFT macro-chaintransfer agent was used in methacrylamide polymerization.32,33
Zhao and co-workers reported on the combination of RAFT
polymerization with click chemistry to attach poly(Nisopropylacrylamide, PNIPAM) brushes onto reduced GO
surfaces, thus rendering graphene brushes thermoresponsive.34
In another work, the group of Zhao presented a simultaneous
coupling reaction and RAFT process to graft dierent polymers
from GO. A RAFT-active trithiocarbonate group terminated
with a trimethoxysilyl moiety was coupled to GO located
hydroxyl groups. After cleavage of the polymers by aminolysis
or HF treatment, narrow weight distributions were found.35
Although thiols are well-known as very powerful chain transfer
agents in free radical polymerization and calculations on thiolfunctionalized graphenes have been reported by Denis,36 to the
best of our knowledge FG thiols have not been used as FG
macro-chain-transfer agents.
Here we report on a very versatile process for the preparation
of sulfur-functionalized Stearyl-GO and TRGO useful as macrochain-transfer and RAFT agents for the free radical grafting of
polystyrene chains onto FG. Melt rheology of conventional
polystyrene/FG melt compounds was compared with that of
polystyrene grafted onto S-FG in order to examine the
inuence of grafting eectiveness on the dispersion and
structure formation, resulting from supramolecular assembly
of FG during melt compounding.

Article

EXPERIMENTAL SECTION

Materials. All synthesis chemicals were purchased from SigmaAldrich, Acros Organics, or Merck. THF (dried over CaH2), toluene
(dried over potassium), and styrene were freshly distilled prior to use.
All the other solvents and chemicals were used without further
purication. TRGO was obtained by thermal reduction of GO at 400
C.37
Instrumentation. The sulfur content of the modied graphene
was determined with a VarioEL elemental analyzer from Elementaranalysensysteme GmbH. FT-IR spectra were measured, using KBr
tablets containing the sample. With a Vektor 22 from Bruker 32 scans
with a resolution of 2 cm1 were recorded. The thermal degradation
was analyzed by means of thermogravimetric analysis (STA 409 from
Netzsch), 50650 C at 10 K/min under nitrogen. The glass
transition temperatures (Tg) were measured by dierential scanning
calorimetry. The samples (510 mg) were heated and cooled in three
cycles in an EXSTAR DSC 6200 R from Seiko Instruments Inc.
Molecular weight and polydispersity were analyzed using a polymer
solution (4 mg/mL in CHCl3) with a PSS-SVDB column at 30 C
using a RI K-2301 and a 1200 UV detector. Rheological measurements
were carried out with an ARES rheometer from Rheometric Scientic.
The rheology specimens (diameter 25 mm) were measured using a
plate/plate geometry. The frequency was varied from 0.1 to 100 rad/s
using a deformation which was consistent with the linear range. The
temperature was varied within the range of 135255 C. Transmission
electron microscopy (TEM) images were made with a Zeiss/LEO 913
W at 120 kV. The samples were microtomed at room temperature and
immobilized on Cu grids.
Synthesis. Graphite Oxide (GO). GO was synthesized by a
modied Hummers method.21 In a typical synthesis, graphite (60.0 g)
and NaNO3 (30.0 g) were dispersed in concentrated H2SO4 (1400
mL) and stirred at ambient temperature for 12 h. The mixture was
cooled to 0 C, and KMnO4 (180.0 g) was added during 2 h. After
stirring for another 5 h at ambient temperature the dispersion was
dumped into ice water (2800 mL) before a H2O2 solution (5%, 300
mL) was added. The raw GO was washed with water for a several
times and afterward was dried in vacuum (400 mbar) at 40 C. The
resulting GO (C = 52.8%, H = 2.4%, O = 44.8%) was used with a
hydroxyl functionality of 26.7 mmol/g (the oxygen content of 44.8%
was set as hydroxyl groups only).
Stearyl-GO. GO (5.0 g) was dispersed in NMP (200 mL). After
heating to 70 C stearylamine (15.0 g) was added and the mixture was
stirred for 3 h at 70 C. The product was ltered o from hot solution
and washed with hot acetone (3 200 mL) for purication. The
obtained Stearyl-GO (content of stearylamine was 1.79 mmol/g) was
dried in a vacuum (10 mbar, 60 C).
FG Dithiocarbonates (FG-DTC). The deprotonation of FG hydroxyl
groups followed by reaction with carbon disulde and benzyl bromide
was performed in dierent solvents varied as a function of the FG
type: NMP (100 mL) for GO, THF (100 mL) for Stearyl-GO, and
toluene (100 mL) for TRGO. After dispersion of the respective
material (1.0 g, 26.7 mmol), dierent bases (26.7 mmol) at ambient
temperature to deprotonate the hydroxyl groups were added. After
successively adding CS2 (1.6 mL, 26.7 mmol) and benzyl bromide
(BnBr, 3.2 mL, 26.7 mmol), the resulting reaction mixture was stirred
at 70 C for 2 h. After ltration and washing with acetone (3 100
mL) the S-FG was dried in vacuum (10 mbar, 60 C) for 2 days.
FG Dithioester (FG-DTE). FG-DTE was prepared in NMP (200
mL) containing dispersed GO (2.0 g, 53.4 mmol). An aryl Grignard
solution (53.4 mmol) in THF (40 mL) was reacted with CS2 (3.2 mL,
53.4 mmol) and added to the GO dispersion. The reaction mixture
was stirred at 65 C for 45 min. After addition of ethanol (3 mL) the
product was ltered o, washed with acetone (3 80 mL), and dried
in vacuum (10 mbar, 40 C).
Thiol-Functional FG. Thiol-functionalized FG was derived from
Stearyl-GO (1.0 g, 26.7 mmol), which was dispersed in CH2Cl2 (100
mL). Then 3-mercaptopropionic acid (2.3 mL, 26.7 mmol), DMAP
(1.6 g, 13.4 mmol), and DCC (23.0 mmol) were added. The mixture
was stirred at ambient temperature for 4 days. After ltration and
7084

dx.doi.org/10.1021/ma301379z | Macromolecules 2012, 45, 70837090

Macromolecules

Article

Scheme 1. Synthetic Strategies toward S-FG and S-FG Brushes

Table 1. Properties of Dierent S-FG Types

sample
GO-DTC-1
GO-DTC-2
GO-DTC-3
GO-DTC-4
Stearyl-GO-RAFT-1
Stearyl-GO-RAFT-2
Stearyl-GO-RAFT-3
Stearyl-GO-RAFT-4
GO-DTE-5
GO-DTE-6
Stearyl-GO-ES-1
Stearyl-GO-S-2
TRGO-S
a

functional group

graphene type

-O-CS-SCH2C6H5

GO

-O-CS-SCH2C6H5
-NH-CS-SCH2C6H5

Stearyl-GO

-S-CS-C6H5
-S-CS-CH2-C6H5-C12H25
-O-CO-(CH2)2-SH
-O-CH2-CH(SH)-CH3
-O-CO-(CH2)2-SH

GO
Stearyl-GO
TRGO

base

S-contenta [mol/kg]

N(iPr)2Et
KOH
NEt3
NaH
N(iPr)2Et
NaH
LDA
n-BuLi

NEt3
LiN(iPr2)

0.05
0.12
0.18
0.27
0.18
0.40
0.54
1.02
0.22
0.29
(2.04)b
0.24
0.43

S content was calculated using the sulfur content, obtained from elemental analysis. bHigh S content owing to side product impurities.

washing with acetone (100 mL) and CH2Cl2 (2 100 mL) the
product was dried in vacuum (10 mbar, 40 C).
The propylene sulde functionalization of TRGO (1.0 g, 26.7
mmol) was carried out in toluene (100 mL) and the functionalization
of Stearyl-GO (1.0 g, 26.7 mmol) in THF (70 mL). After dispersion
and deprotonation with dierent bases (23.9 mmol) at ambient
temperature propylene sulde (2.1 mL, 26.7 mmol) was added. The
mixture was stirred at 60 C for 3 h. After ltration and washing with
acetone (3 100 mL) the product was dried in vacuum (10 mbar, 40
C).
Polystyrene Grafting of S-FG (General Procedure). Typical
procedure for AIBN-initiated grafting: Various amounts of the S-FG
were dispersed in styrene (freshly distilled, 9.1 g, 10 mL) by
sonication. In some cases NMP was added as solution mediator. Then
various amounts of AIBN were added, and the mixture was degassed
by three freezepumpthaw cycles. The polymerization was carried
out at 65 C in a nitrogen atmosphere. Then the reaction mixture was
diluted with CHCl3 (100 mL) and centrifuged (8500 rpm, 1 h). The
supernatant was precipitated in methanol (800 mL), and the
resulting powder was dried in vacuum (10 mbar, 70 C).

In a typical procedure for the thermal self-initiated grafting, S-FG

(500 mg, 5.5 wt %) was dispersed in styrene (freshly distilled, 9.1 g, 10
mL) by sonication. After degassing the mixture with three freeze
pumpthaw cycles the polymerization was carried out at 130 C for
17 h under a nitrogen atmosphere. Then the reaction mixture was
diluted with CHCl3 (100 mL), followed by centrifugation (8500
rpm, 1 h). The supernatant was precipitated in methanol (800 mL),
and the gained composite was dried in vacuum (10 mbar, 70 C). The
properties of the polystyrene grafted S-FG are summarized in Table 2.

RESULTS AND DISCUSSION

Preparation of Sulfur-Functionalized Graphenes as
Macro-Chain-Transfer Agents. Sulfur-functionalized graphenes (S-FG) containing thiol, dithioester, dithiourethane, and
dithiocarbonate groups were prepared from graphite oxide
(GO), stearylamine-modied GO (Stearyl-GO), and thermally
reduced graphite oxide (TRGO). In contrast to the hydrophilic
GO (45.9% carbon content), Stearyl-GO with a carbon content
of 72 wt % and a stearyl functionality of 1.79 mmol/g was easy
7085

dx.doi.org/10.1021/ma301379z | Macromolecules 2012, 45, 70837090

Macromolecules

Article

procedures reported in the literature31,42 using 3-mercaptopropionic acid (26.7 mmol, 1.0 equiv), DMAP (0.38 equiv), and
DCC (0.86 equiv) in CH2Cl2. Although the ester formation is
conrmed by FT-IR spectroscopy and high sulfur content of
2.04 mol/kg (Stearyl-GO-ES-1) was achieved, purication and
complete removal of dicyclohexyl urea side product were rather
dicult. Therefore, in pathway D (Scheme 1), an alternative
route to thiol-FG was developed without such requiring tedious
purication. The hydroxyl groups of Stearyl-GO and TRGO
were deprotonated, and the resulting alcoholates were reacted
with propylene sulde to produce thiols via nucleophilic
addition and subsequent ring-opening of the thiiran ring.
Similar to the results reported above, the stronger base lithium
diisopropylamide (LDA) with respect to triethylamine gave
higher SH functionality, which was found to be 0.43 mol/kg.
The thiol functionalization was conrmed by means of FT-IR
spectroscopy (see Figure 2), showing typical CS vibration
modes at 10001200 cm1. Only for Stearyl-GO-SH-2, the C
S vibrations were overlapped by Stearyl-GO modes.

to disperse in styrene and most solvents used in free radical

polymerization.38,39 Upon ash pyrolysis of GO at 400 C, GO
decomposes and the evolved gases such as CO and CO2 cause
expansion of GO, as reected by much higher BET surface area
of 348 m2/g and higher carbon content of 60.3% compared to
the pristine GO. The four basic synthetic strategies for sulfur
functionalization of GO, Stearyl-GO, and TRGO are outlined
in Scheme 1.
In pathway A (Scheme 1) the FG hydroxyl groups were
deprotonated and converted with carbon disulde into the
dithiocarbonate salts, which are alkylated with benzyl bromide
to aord the corresponding benzyldithiocarbonate groups. As it
is apparent from Table 1, the S group content increased
markedly with increasing strength (pKb) of the bases. Highest S
group content was obtained when using strong bases such as
NaH and BuLi for the deprotonation of FG hydroxyl groups. In
comparison to GO, the Stearyl-GO gave much higher S
content. Most likely, this results from better compatibility as
well as the simultaneous reaction of the secondary amines with
carbon disulde, producing dithiocarbonates together with
dithiourethanes on FG. In pathway B (Scheme 1), the phenyl
and p-dodecylbenzyl Grignard reagent were reacted with
carbon disulde to produce phenyl- and benzyldithiocarboxylates which were reacted with the epoxy groups of GO. The
resulting S content was rather low. Although the GO epoxy
groups are known to react with nucleophiles,25 the epoxy group
content is much lower with respect to the hydroxyl group
content. Moreover, it should be noted that GO is an oxidative
agent which can oxidize dithiocarboxylates to produce detached
disuldes, which are removed during purication steps. The
detected S functionalities were much lower than expected from
the oxygen content. This was due to the fact that the oxygen
content of 26.7 mol/kg does not represent the ratio of chemical
available hydroxyl groups, but rather all kinds of oxygen groups
bound on FG.
All S-FG were analyzed by means of FT-IR spectroscopy
detecting the characteristic CS and CS vibration bands
between 1000 and 1300 cm1 40,41 (see Figure 1). Because the

Figure 2. FT-IR spectra of (a) Stearyl-GO (), (b) Stearyl-GO-S-2

(), (c) TRGO (- - -), and (d) TRGO-S (- -).

Thermogravimetric analysis (TGA) was used to compare the

thermal stability of S-FG with respect to that of GO, TRGO,
and Stearyl-GO. Upon heating to 650 C, S-FG based upon
GO and TRGO show higher weight loss in comparison to the
S-free graphenes, as expected when incorporating the thermally
more labile sulfur groups. The TRGO-based systems have
much higher thermal stability with respect to GO and StearylGO because TRGO was thermally reduced at 400 C, whereas
GO is thermally reduced during the TGA measurement, as
illustrated by the massive weight loss above 150 C. In the case
of Stearyl-GO the thermal degradation is more complex. Most
likely, the modication with stearylamine and the subsequent
functionalization are accompanied by partial chemical reduction
of GO, which could account for the slightly higher residual
mass of sulfur-modied Stearyl-GO at 650 C (see Figure 3).
Grafting Polystyrene onto S-FG. As illustrated in Scheme
1, the S-FG agents were added to the free radical polymerization of styrene. The free radical polymerization was initiated
either by addition of the azoisobutyronitrile (AIBN) initiator at
65 C or by means of the initiator-free thermal self-initiation of
styrene polymerization at 130 C.43,44 The sample code (r)
denotes AIBN initiation, whereas (t) marks the thermal selfinitiation in the absence of initiator. In order to separate S-FG
from polystyrene-grafted S-FG, the reaction mixture was
diluted with chloroform and S-FG was removed by means of
a centrifuge, whereas the dispersion of grafted S-FG was much

Figure 1. FT-IR spectra of (a) GO (), (b) GODTC-4 (- - -), and

(c) Stearyl-GO-RAFT-3 ().

GO, Stearyl-GO, and TRGO exhibit no absorption in this area,

IR spectroscopy represents a powerful analytic tool conrming
the formation of the dithiocarbonates and dithiourethanes on
FG.
In pathway C (Scheme 1) thiol groups were introduced by
DCC/DMAP-mediated esterication of the Stearyl-GO
hydroxyl groups with 3-mercapropropionic acid, following
7086

dx.doi.org/10.1021/ma301379z | Macromolecules 2012, 45, 70837090

Macromolecules

Article

styrene and no NMP addition was required. The resulting

polystyrene nanocomposites exhibited Tg varying around 107
C. No clear correlation was found between the ratio of styrene
to macro-chain-transfer agent and the residual mass, detected
upon heating the puried samples to 650 C (Table 2).
In order to examine the role of polystyrene grafting and
covalent attachment of PS on S-FG, the dithiocarbonate linkers
were cleaved by hydrolysis in the presence of aqueous
potassium hydroxide at 85 C, similar to procedures reported
previously for other polystyrene graft copolymers.45 As it is
apparent from Figure 4, the cleavage of the linker destroys the

Figure 3. Thermal degradation, as measured by thermogravimetric

analysis (TGA), of S-FG based upon GO (), Stearyl-GO (), and
TRGO (- - -).

less sensitive to sedimentation. Only the supernatant solution

was precipitated in methanol in order to recover the S-FG
polystyrene nanocomposites. The graphene content was
determined as residual mass upon heating at 600 C in
thermogravimetric analysis. The results are listed in Table 2.
Because of the rather poor dispersibility of GODTC in
styrene, the addition of N-methylpyrrolidinone (NMP) was
required in some cases. During radical polymerization, chain
transfer as well as additionfragmentation reactions enabled
the growth of polystyrene onto S-FG in those systems.
Typically for GO-DTC the S-FG content was varied between
2.7 and 5.5 wt % using AIBN concentration varying between
0.7 and 1.3 mol %. In comparison to FG-free polystyrene PS(r),
prepared under similar conditions, all GO-DTC systems
increased glass transition temperatures (Tg) ranging between
103 and 107 C. This is in accord with observations in the
literature, reporting Tg increases up to 10 C in the case of
successful grafting.27 Because of the covalent attachment of
polystyrene to the ultrathin but micrometer-sized graphenes,
molar mass determination by means of size exclusion
chromatography (SEC) was not possible. The graphene-free
reference PS(r) had molar mass of Mw = 41.0 kg/mol. In
contrast to GO-DTC, Stearyl-GO-RAFT was easily dispersed in

Figure 4. Image of PS-Stearyl-GO-RAFT(r) before (left) and after

(right) hydrolysis of the linker.

excellent stability of the S-FG dispersion in polystyrene, which

leads to a phase separation. The nonbonded S-FG is readily
removed quantitatively from polystyrene by means of a
centrifuge. Afterward, the detached, pristine polystyrene was
precipitated, giving a clear white powder. The average Mw of
the resulting polystyrene after linker cleavage was determined
to be 30.4 kg/mol with a polydispersity of 5.0.
The thiol-functionalized macro-chain-transfer agents were
grafted exclusively by thermal self-initiation at 130 C. After
purication, the resulting residual masses of the puried

Table 2. Properties of the S-FG Graft Copolymers

samplea

initial S-FG content [wt %/mmol Sfunct]

yield [g/%]

Tg (DSC) [C]

residual mass (650 C) [%]

PS(r)
PS-GO-DTC-2(r)b
PS-GO-DTC-3(r)b
PS-GO-DTC-1(r)b
PS-GO-DTE-5(r)
PS-GO-DTC-4(r)
PS-GO-DTE-6(t)
PS-Stearyl-GO-RAFT-1(r)
PS-Stearyl-GO-RAFT-2(r)
PS(t)
PS-Stearyl-GO-RAFT-2(t)
PS-Stearyl-GO-RAFT-4(t)
PS-Stearyl-GO-RAFT-3(t)
PS-Stearyl-GO-S-2(t)
PS-Stearyl-GO-ES-1(t)
PS-TRGO-S(t)

1.1/0.048
1.1/0.072
2.8/0.013
5.5/0.110
5.5/0.135
5.5/0.290
2.8/0.045
11.0/0.100

5.5/0.399
5.5/1.015
5.5/0.541
5.5/0.243
5.5/2.036
5.5/0.434

31.6/87
8.3/91
7.4/81
4.7/21
8.8/97
6.5/71
6.6/73
8.0/88
8.0/88
7.9/87
7.8/86
7.8/86
7.1/78
7.5/82
7.6/84
8.1/89

95.0
104.8
103.4
105.4
107.2
100.6
106.5
107.8
108.2
107.5
107.4
106.1
105.9
106.2
102.5
108.2

0.0
0.5
0.5
2.6
5.0
2.9
1.5
2.1
1.0
0.0
2.0
2.3
3.1
5.2
3.4
2.3

(r): radical polymerization at 65 C (AIBN initiated); (t): radical polymerization at 130 C (styrene self-initiated). bPolymerization with the use of
NMP.

7087

dx.doi.org/10.1021/ma301379z | Macromolecules 2012, 45, 70837090

Macromolecules

Article

processing for 2 min at 220 C. The solution blend was

produced by sonication of a Stearyl-GO/polystyrene dispersion
in toluene followed by heating to 130 C for 15 h and
precipitating in methanol. As is apparent from Figure 5a, the
melt blending of Stearyl-GO fails to produce ne dispersions
typical for the grafted samples.
Melt rheology is a powerful tool to characterize network-like
superstructures such as formed by S-FG brushes in polystyrene.
Therefore, the van GurpPalmen plot46 makes it easy to dier
between conventional polymers, showing ideal viscous
behavior, and polymers with a particle network. Without
covalent attachment, the van GurpPalmen plot ( vs |G*|)
conrms that the timetemperature superposition principle
applies and shows that the melt-blend rheology is matrix
dominated. As a consequence, all values converge together into
one curve approaching 90 for small |G*| values. For network
formation a decreasing curve progression at small |G*| values is
observed, indicating the equilibration modulus |G*eq(T)|

Scheme 2. Cleavage of the Dithiocarbonate Linkers of the SFG Brushes by Hydrolysis with KOH

nanocomposites were high and varied between 2.3% and 5.2%.

This is an indication that grafting was highly eective. With
exception of PS-Stearyl-GO-SH-1(t), the resulting S-FG
nanocomposites exhibited Tg around 107 C, as observed
previously for the other S-FG brushes.
Rheology and Morphology Development. In order to
examine the role of grafting on S-FG dispersions, Stearyl-GO
was melt blended, as well as solution blended, together with
commercial polystyrene (PS 158K, Mw = 2.6 105 g/mol, PDI
= 2.5). The melt-compound was produced with a microcompounder (Type 20000 from Daca Instruments) by

Figure 5. TEM images (left) and related van GurpPalmen plots (T = 135255 C) of (a) PS 158K melt compound (2.5 wt % Stearyl-GO), (b) an
in situ grafted PS-Stearyl-GO-RAFT-3(t) (3.1 wt %), and (c) PS-Stearyl-GO solution blend (2.5 wt % Stearyl-GO). Solid lines in the van Gurp
Palmen plot represents the (a) pristine PS-behavior and (b, c) the extrapolated equilibration modulus |G*eq(T)|.
7088

dx.doi.org/10.1021/ma301379z | Macromolecules 2012, 45, 70837090

Macromolecules

Article

CONCLUSION
In conclusion, four synthetic strategies were developed for
enabling the conversion of hydroxyl and amine groups of GO,
Stearyl-GO, and TRGO into thiol, dithioester, dithiocarbonate,
and dithiourethane groups useful as macro-chain-transfer agent
for growing polystyrene chains onto S-FG. According to
elemental analysis, TGA, and FT-IR spectroscopy, strong bases
aord very eective deprotonation of FG hydroxyl groups
which can react with carbon disulde, followed by alkylation, to
produce RAFT reagents. In an alternative process, propylene
sulde was added to FG alkoxides to produce FG-thiols. Both
FG-RAFT and FG-thiols were highly eective as chain-transfer
agents in free radical polymerization, initiated either with AIBN
initiator or by means of thermal self-initiation at 130 C. Only
in the presence of covalent attachment of S-FG to polystyrene,
stable S-FG dispersions in polystyrene melts were obtained.
Cleavage of the dithiocarbonate linkers in FG-RAFT systems
destroyed the stability of S-FG dispersions and enabled
quantitative removal of S-FG. To verify the covalent attachment of polystyrene chains to S-FG, rheological measurements
plotting as a function of |G*| in the van GurpPalmen plot
have enabled the monitoring of a temperature-dependent
network-like structure development. Highly eective grafting
and formation of FG brushes were exclusively observed for
stearyl-modied GO. Both conventional melt and solution
blending of Stearyl-GO with polystyrene failed to produce
particle networks in the absence of covalent coupling.

founded by the platelets network. This distinct dierence in

rheological behavior was found for the polystyrene nanocomposites prepared by in situ polymerization and grafting,
whereas the melt blend and some free radical polymerized SFG composites showed a behavior similar to the pristine
polystyrene (Figure 5a).
The stearyl-modied S-FG brushes showed the formation of
a temperature-dependent network-like structure expressed by
the decreasing curve type in Figure 5b. This is in accord with
the results of the TEM investigation that only the polystyrenegrafted graphenes exhibit network-like superstructures.
To check the covalent attachment of polystyrene chains, the
results above were compared to the PS-Stearyl-GO solution
blend (see Figure 5c). Because of the homogeneous dispersion,
the van GurpPalmen plot showed a temperature-independent
particle network formation by the decreasing behavior of for
little values of |G*|. This observation is in accord with previous
studies on the very similar rheological behavior of organoclay
nanosheets containing covalently and ionically attached
polystyrene47 and polypropylene.48 In contrary to the reported
systems, a thermal equilibration without shearing was
impossible in case of the in situ grafted composites. In
addition, an aggregation of the grafted particles due to the
instability of thiol-modied polymer ligands, as observed by Li
and co-workers, who studied polymerthiol grafted gold
nanoparticles,49 was not detected.
Table 3 shows the results of the melt rheological measurements, including the residual mass detected by the means of

Table 3. Rheological Properties of Dierent S-FG

Polystyrene Composites and Reference Systems

AUTHOR INFORMATION

Corresponding Author

*E-mail: rolf.muelhaupt@makro.uni-freiburg.de.

nanocomposite

residual massa [%]

network formation

PS-GO-DTC-4(r)
PS-GO-DTE-5(r)
PS-GO-DTE-6(t)
PS-Stearyl-GO-RAFT-2(r)
PS-Stearyl-GO-ES-1(t)
PS-TRGO-S(t)
PS-Stearyl-GO-RAFT-1(r)
PS-Stearyl-GO-RAFT-4(t)
PS-Stearyl-GO-RAFT-3(t)
PS-Stearyl-GO-S-2(t)
PS-Stearyl-GO melt blend
PS-Stearyl-GO solution blend

2.9
5.0
1.5
1.0
3.4
2.3
2.1
2.3
3.1
5.2
2.5b
2.5b

Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
The authors gratefully acknowledge the nancial support by the
Federal Ministry of Education and Research (BMBF) as part of
the FUNgraphen project (project 03X0111A). The authors also
thank Dr. R. Feher for a lot of helpful discussions and the
supply of graphite.

REFERENCES

(1) Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang,
Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Science 2004, 306
(5696), 666669.
(2) Boehm, H. P. Z. Naturforsch. 1962, 17b, 150153.
(3) Geim, A. K.; Novoselov, K. S. Nat. Mater. 2007, 6 (3), 183191.
(4) Li, X.; Cai, W.; An, J.; Kim, S.; Nah, J.; Yang, D.; Piner, R.;
Velamakanni, A.; Jung, I.; Tutuc, E.; Banerjee, S. K.; Colombo, L.;
Ruoff, R. S. Science 2009, 324 (5932), 13121314.
(5) Gomez De Arco, L.; Zhang, Y.; Schlenker, C. W.; Ryu, K.;
Thompson, M. E.; Zhou, C. ACS Nano 2010, 4 (5), 28652873.
(6) Wang, S.; Ang, P. K.; Wang, Z.; Tang, A. L. L.; Thong, J. T. L.;
Loh, K. P. Nano Lett. 2009, 10 (1), 9298.
(7) Robinson, J. T.; Perkins, F. K.; Snow, E. S.; Wei, Z.; Sheehan, P.
E. Nano Lett. 2008, 8 (10), 31373140.
(8) Bunch, J. S.; Verbridge, S. S.; Alden, J. S.; van der Zande, A. M.;
Parpia, J. M.; Craighead, H. G.; McEuen, P. L. Nano Lett. 2008, 8 (8),
24582462.
(9) Kim, K. S.; Zhao, Y.; Jang, H.; Lee, S. Y.; Kim, J. M.; Kim, K. S.;
Ahn, J.-H.; Kim, P.; Choi, J.-Y.; Hong, B. H. Nature 2009, 457 (7230),
706710.
(10) Imran Jafri, R.; Rajalakshmi, N.; Ramaprabhu, S. J. Mater. Chem.
2010, 20 (34), 71147117.

Residual mass detected by the means of thermogravimetric analysis.

Melt and solution blends contained an initial content of 2.5 wt %
Stearyl-GO.

thermogravimetric analysis and the qualitative particle network

formation. The melt and solution blends were synthetized with
an initial Stearyl-GO content of 2.5 wt %.
The data in Table 3 indicate that a network formation was
only observed in the cases of stearyl-modied S-FG. This is
attributed to the substantially improved dispersion of StearylGO with respect to GO, causing percolation and formation of a
network-like superstructure. Poor dispersions did not permit
experimental verication of grafting for the other materials
based upon S-FG. In our case, the results of melt rheological
measurements enabled the supervision of a covalent attachment
because grafting leads to a highly improved graphene
dispersibility causing percolation and the characteristic behavior
showed in the van GurpPalmen plot.
7089

dx.doi.org/10.1021/ma301379z | Macromolecules 2012, 45, 70837090

Macromolecules

Article

(11) Li, D.; Muller, M. B.; Gilje, S.; Kaner, R. B.; Wallace, G. G. Nat.
Nanotechnol. 2008, 3 (2), 101105.
(12) Kim, H.; Abdala, A. A.; Macosko, C. W. Macromolecules 2010,
43 (16), 65156530.
(13) Steurer, P.; Wissert, R.; Thomann, R.; Mulhaupt, R. Macromol.
Rapid Commun. 2009, 30 (45), 316327.
(14) Salavagione, H. J.; Martnez, G.; Ellis, G. Macromol. Rapid
Commun. 2011, 32 (22), 17711789.
(15) Xiao, P.; Xiao, M.; Gong, K. Polymer 2001, 42 (11), 48134816.
(16) Wu, H.; Zhao, W.; Hu, H.; Chen, G. J. Mater. Chem. 2011, 21
(24), 86268632.
(17) Zhao, W.; Fang, M.; Wu, F.; Wu, H.; Wang, L.; Chen, G. J.
Mater. Chem. 2010, 20 (28), 58175819.
(18) Zheng, H.; Jiang, K.; Abe, T.; Ogumi, Z. Carbon 2006, 44 (2),
203210.
(19) Dreyer, D. R.; Park, S.; Bielawski, C. W.; Ruoff, R. S. Chem. Soc.
Rev. 2009, 39 (1), 228240.
(20) Brodie, B. C. Philos. Trans. R. Soc. London 1859, 149, 249259.
(21) Hummers, W. S.; Offeman, R. E. J. Am. Chem. Soc. 1958, 80 (6),
13391339.
(22) Schniepp, H. C.; Li, J.-L.; McAllister, M. J.; Sai, H.; HerreraAlonso, M.; Adamson, D. H.; Prudhomme, R. K.; Car, R.; Saville, D.
A.; Aksay, I. A. J. Phys. Chem. B 2006, 110 (17), 85358539.
(23) Zhu, Y.; Murali, S.; Cai, W.; Li, X.; Suk, J. W.; Potts, J. R.; Ruoff,
R. S. Adv. Mater. 2010, 22 (35), 39063924.
(24) Stankovich, S.; Dikin, D. A.; Dommett, G. H. B.; Kohlhaas, K.
M.; Zimney, E. J.; Stach, E. A.; Piner, R. D.; Nguyen, S. T.; Ruoff, R. S.
Nature 2006, 442 (7100), 282286.
(25) Bourlinos, A. B.; Gournis, D.; Petridis, D.; Szabo, T.; Szeri, A.;
Dakany, I. Langmuir 2003, 19 (15), 60506055.
(26) Lee, S. H.; Dreyer, D. R.; An, J.; Velamakanni, A.; Piner, R. D.;
Park, S.; Zhu, Y.; Kim, S. O.; Bielawski, C. W.; Ruoff, R. S. Macromol.
Rapid Commun. 2010, 31 (3), 281288.
(27) Fang, M.; Wang, K.; Lu, H.; Yang, Y.; Nutt, S. J. Mater. Chem.
2009, 19 (38), 70987105.
(28) Pramoda, K. P.; Hussain, H.; Koh, H. M.; Tan, H. R.; He, C. B.
J. Polym. Sci., Part A: Polym. Chem. 2010, 48 (19), 42624267.
(29) Barner-Kowollik, C. Handbook of RAFT-Polymerization; WileyVCH Verlag GmbH & Co. KGaA: Weinheim, 2008.
(30) Etmimi, H. M.; Tonge, M. P.; Sanderson, R. D. J. Polym. Sci.,
Part A: Polym. Chem. 2011, 49 (7), 16211632.
(31) Zhang, B.; Chen, Y.; Xu, L.; Zeng, L.; He, Y.; Kang, E.-T.;
Zhang, J. J. Polym. Sci., Part A: Polym. Chem. 2011, 49 (9), 20432050.
(32) Li, Y.; Li, X.; Dong, C.; Qi, J.; Han, X. Carbon 2010, 48 (12),
34273433.
(33) Li, Y.; Li, X.; Dong, C.; Li, Y.; Jin, P.; Qi, J. Biosens. Bioelectron.
2009, 25 (2), 306312.
(34) Yang, Y.; Song, X.; Yuan, L.; Li, M.; Liu, J.; Ji, R.; Zhao, H. J.
Polym. Sci., Part A: Polym. Chem. 2011, 50 (2), 329337.
(35) Jiang, K.; Ye, C.; Zhang, P.; Wang, X.; Zhao, Y. Macromolecules
2012, 45 (3), 13461355.
(36) Denis, P. A. J. Phys. Chem. C 2009, 113 (14), 56125619.
(37) Tolle, F. J.; Fabritius, M.; Mulhaupt, R. Adv. Funct. Mater. 2012,
22 (6), 11361144.
(38) Ranjbartoreh, A. R.; Wang, B.; Shen, X.; Wang, G. J. Appl. Phys.
2011, 109, 014306.
(39) Niyogi, S.; Bekyarova, E.; Itkis, M. E.; McWilliams, J. L.;
Hamon, M. A.; Haddon, R. C. J. Am. Chem. Soc. 2006, 128 (24),
77207721.
(40) Hellstrom, P.; Holmgren, A.; A berg, S. J. Phys. Chem. C 2007,
111 (45), 1692016926.
(41) Bak, B. Acta Chem. Scand. 1958, 12, 14511455.
(42) Neises, B.; Steglich, W. Angew, Chem. Int. Ed. 1978, 17 (7),
522524.
(43) Flory, P. J. J. Am. Chem. Soc. 1937, 59 (2), 241253.
(44) Mayo, F. R. J. Am. Chem. Soc. 1968, 90 (5), 12891295.
(45) Ferjancic, Z.; Quiclet-Sire, B.; Zard, S. Z. Synthesis 2008, 2008
(18), 29963008.
(46) van Gurp, M.; Palmen, J. Rheol. Bull. 1998, 67, 58.

(47) Hoffmann, B.; Dietrich, C.; Thomann, R.; Friedrich, C.;

Mulhaupt, R. Macromol. Rapid Commun. 2000, 21 (1), 5761.
(48) Reichert, P.; Hoffmann, B.; Bock, T.; Thomann, R.; Mulhaupt,
R.; Friedrich, C. Macromol. Rapid Commun. 2001, 22 (7), 519523.
(49) Zhu, M.-Q.; Wang, L.-Q.; Exarhos, G. J.; Li, A. D. Q. J. Am.
Chem. Soc. 2004, 126 (9), 26562657.

7090

dx.doi.org/10.1021/ma301379z | Macromolecules 2012, 45, 70837090