Carbon 95 (2015) 780e788

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Carbon
journal homepage: www.elsevier.com/locate/carbon

Synthesis and characterization of high-softening-point methylenebridged pitches by visible light irradiation assisted free-radical
bromination
Chuanzhang Ge a, Haixiao Yang a, Jin Miyawaki b, Isao Mochida b, Seong-Ho Yoon b, **,
Wenming Qiao a, Donghui Long a, *, Licheng Ling a
a
b

State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
Institute for Materials Chemistry and Engineering, Kyushu University, Kasuga, Fukuoka 816-8580, Japan

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 9 April 2015
Received in revised form
27 August 2015
Accepted 1 September 2015
Available online 4 September 2015

A novel methylene-bridged polymeric pitch was successfully synthesized from 1-methylnaphthalene (1MNP) using bromine as a sacricial agent for CeC bond construction. 1-MNP was reacted with bromine
in the presence of strong visible light irradiation (40e70 kcal/mol), yielding exclusively side-chain
substituted 1-methylnaphthalene (M-Br). After a thermal dehydrobromination/polycondensation reaction at 200e270
C, high quality carbonaceous isotropic pitches with a softening point of 196e250
C
were obtained. The optimized factors inuencing the photobromination, including reaction temperature,
substrate concentration and properties of solvents were determined. The dehydrobromination reaction
kinetic followed a pseudo-rst-order reaction model with apparent reaction activation energy of
122.6 kJ/mol. The as-prepared polymeric pitches consisted of numbers of repeated monomers with a
linear structure of methylene bridged naphthalene rings. The unique structure of the pitches resulted in
high value of C/H ratio, high molecular weight and 100% soluble in toluene. Moreover, the pitches
exhibited very low viscosity at temperatures near the softening point, and their viscosities experienced a
unique transition from shear-thinning to shear-thickening and then to shear-thinning process. The coke
obtained from short molecular pitch by carbonizing at 550
C show an anisotropic phase of ow domains
both in atmospheric pressure and pressured conditions.
2015 Elsevier Ltd. All rights reserved.

Keywords:
Polymeric pitch
Bromination
Dehydrobromination
Properties
Carbonization

1. Introduction
Carbonaceous pitches are mixtures of polycyclic aromatic hydrocarbon (PAH) oligomers which exhibit a broad molecular weight
distribution (MWD) ranging from 200 to 1600 [1]. They have
properties of high carbon yield and solvent solubility, and the potential for further forming carbonaceous mesophase [2], thus being
wildly used as precursors for various high-value carbon products,
such as graphite foams [3], carbon bers [4,5], advanced carbon/
carbon composites [6,7] and cathode materials for lithium ion
batteries [8,9]. Because raw, untreated pitches have such a broad
MWD, they do not always have the desired bulk properties (e.g.,

* Corresponding author.
** Corresponding author.
E-mail addresses: yoon@cm.kyushu-u.ac.jp (S.-H. Yoon), longdh@mail.ecust.edu.
cn (D. Long).
http://dx.doi.org/10.1016/j.carbon.2015.09.003
0008-6223/ 2015 Elsevier Ltd. All rights reserved.

softening points above 200
C, high solubility, high carbon yield

and easily oxidizable) for making carbon materials. Thus, a
tremendous amount of techniques have been developed for preparing high-softening-point pitches, basically focusing on the
extraction, thermal and catalytic polymerization of low molecular
hydrocarbons, such as coal tar or petroleum residues. In addition,
pure PAH monomers such as naphthalene, methylnaphthalene,
anthracene and pyrene can also be used as raw materials for producing ultrahigh-purity polymeric pitches. Comparing with coal tar
pitch or petroleum pitch, the using of pure aromatic substances has
features of highly aromatic, essentially free from heteroatoms and
inorganic ash and high pitch quality and consistency. However,
because of low reactivity of pure PAH, the thermal polymerization
usually needs to be hold under severe conditions (high temperature
and high pressure) and result in low conversion [10e13]. Mochida
et al. [14e16] condensed PAH under mild conditions by using
various catalysts. They reported that isotropic pitch could be prepared through condensation from naphthalene with alkali metals

C. Ge et al. / Carbon 95 (2015) 780e788

catalysts [14], and the mesophase pitch from that with Lewis acid
catalysts, such as AlCl3 [15] or HF/BF3 [16]. However, the AlCl3 in
pitches cannot be removed easily due to the high viscosity of the
condensed hydrocarbon, which could cause pufng in the process
of carbonization. The use of HF/BF3, was successful in catalyzing the
pyrolysis reactions of well-dened PAH like naphthalene or
methylnaphthalene. This type of catalyst could easily be removed
from the reaction product, but it was extremely corrosive and
difcult to handle. Therefore, developing new ways of preparing
high performance pitches have been always pursuing for both academic and industrial interests.
Recently, Yoon et al. [17] reported a new thermal bromination/
dehydrobromination method to prepare high performance pitch
with an appropriate softening point by chemical reaction of 2methylnaphthalene with bromine followed by dehydrobromination/polycondensation. The introduction of bromine could induce
intermolecular cross-link of aromatic hydrocarbons through
dehydrogenation polycondensation. Comparing with the conventional thermal polymerization or HF/BF3 catalytic processes, the
bromination/dehydrobromination method was relatively tender
and controllable. The obtained pitch consisted of linear methylene
chains of polycondensed aromatic molecules, which can be used as
suitable precursor for spinning carbon bers and carbon nanober
web. However, since the naphthalene ring bromination is always
competed with the bromination of saturated groups, the direct
thermal bromination of methylnaphthalenes with molecular
bromine resulted in the formation of complex mixture, including
the bromine substituted on the naphthalene rings, side-chain
substituted products and dibromo-derivatives. These substituted
mixtures inevitably affect the structure and properties of the obtained pitch and carbon products. Therefore, how to selectively
brominate to yield almost exclusively side-chain substituted
methylnaphthalene and resulting highly linear pitch is still a
challenge task.
Taussig et al. [18] reported the photobromination of 1methylnaphthalene (1-MNP) with different number of bromine
equivalents could yield mono-to dibromomethyl derivatives.
However, other factors which may affect the formation of monobromomethyl product were not shown in the work. In the present
study, we demonstrated that visible light irradiation assisted selective photobromination (VIPB) could yield almost exclusively
side-chain mono-substituted 1-MNP under mild conditions. The
factors inuencing the photobromination, such as reaction temperature, substrate concentration and properties of solvents, were
investigated.
After
a
thermal
dehydrobromination/polycondensation reaction, high quality carbonaceous isotropic pitches
were achieved from 1-MNP. Compared to the direct thermal
bromination [17], methyl bromination was easily realized from
VIPB in very lower temperature and higher usage of bromine. Also,
the dehydrobromination/polycondensation reaction of the methyl
brominated 1-MNP can be realized in temperature lower than
270
C. The prepared pitches show a narrow molecular weight
distribution with 100% solubility in toluene. The chain growing of
1-MNP by dehydrobromination/polycondensation reaction results
in a linear molecular structure. Such unique pitch should be
excellent precursor for various carbon products as indicated by the
rheological analysis and carbonization behavior study.
2. Experimental
2.1. Preparation of the methylene-bridged pitches
1-MNP (97%, Acros Organics) and liquid bromine (AR, Shanghai
Lingfeng Chemical Reagent Co., Ltd.) were used as feedstock
without further purication. AR grade n-heptane, chloroform and

781

tetrachloromethane were used as the reaction solvents for the

bromination.
The preparation of the methylene-bridged pitches was started
from the bromination of 1-MNP by visible light irradiation assisted
photobromination. The reaction was carried out in a 250 mL threenecked round-bottomed Pyrex glass ask (TPF) equipped with a
reux condenser. In a typical run, 28.4 g 1-MNP was added to the
TPF with a certain amount of solvent to adjust the substrate to
2 mol/L by vigorous agitation. The power changeable xenon lamp
(PLS-SXE300, Beijing Trusttech Co. Ltd., China) equipped with an
ultraviolet cutoff filter was employed to produce visible light
(l  400 nm). The bromine was blown into the TPF from the bottom
by a carrier gas ow of 100 mL/min nitrogen. The exhaust acid gas
was absorbed by saturated sodium hydroxide solution. After the
addition of bromine, the reactor was continuously stirred for
another 30 min under the light. The product was separated by rotary evaporation and the solvent was recycled.
After the optimal methyl bromination condition established, a
scale-up preparation was carried out under the condition. The high
purity M-Br was obtained by distilling the crude product under
vacuum (0.025 mmHg) and collecting the fraction between 110
C
and 130
C. Then the dehydrobromination/polycondensation reaction of puried M-Br was carried out under 200
C, 230
C, 250
C
and 270
C for total duration of 32 h, 9 h, 7.5 h and 2.5 h, respectively. The nal pitch was extracted by n-hexane to eliminate light
constituents. The resulted pitches were noted as T200, T230, T250
and T270 respectively.
2.2. Carbonization procedure
To investigate the coking performance of the as-prepared
pitches, about 1 g of sample T200 and T270 were carbonized in a
horizontal quartz tube (500 mm long, 30 mm diameter) at 550
C
for 2 h under a nitrogen ow of 100 mL/min at atmospheric pressure at a heating rate of 10
C/min. The effect of pressure on the
carbonization was also studied and carried out in a stainless tube at
550
C for 2 h under 1.1 and 3.1 MPa of nitrogen at a heating rate of
5
C/min.
2.3. Characterization
The kind of bromination products and their distributions were
determined by GC/MS instrument (Shimadzu GCMS-QP2010 plus).
The DB-5 ms capillary column (30 m  0.32 mm i.d., lm thickness
0.25 mm) was used for separation. A split/splitless injector was
used. With toluene as solvent, samples of 1 mL were injected into
the injector with a split ratio of 1:30. Oven temperature was kept at
100
C for 5 min, then increasing to 260
C at a rate of 7
C/min and
holding for 3 min. The inlet temperature was kept at 300
C and
helium was used as a carrier gas. The mass conditions were as
follows: ionization voltage: 70 eV; ion source temperature: 250
C;
full scan mode in the m/z range 35e800 with a 0.30 s/scan velocity.
The calibration curves of each fraction in the bromination products
were established for quantitative analysis by using the standard
substance.
The carbon and hydrogen contents of the dehydrobromination
products were obtained by using an elemental analyzer (elementar
vario EL III, Germany). The residual bromine content was calculated
by the difference.
The solubility of the prepared pitch was evaluated by Soxhlet
extraction using toluene. The softening points of the extracted
pitches were measured by thermomechanical analysis (DMA2980,
America). The pitch sample was heated from ambient to 300
C at
5
C/min in nitrogen atmosphere and the pressure exerted by the
probe on the surface of the pitch was 0.001 N.

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C. Ge et al. / Carbon 95 (2015) 780e788

1
H NMR spectrums were measured using a Bruker Avance 400
spectrometer (400 MHz), and the sample solutions were prepared
with methylene chloride-d2 using tetramethylsilane (TMS) as an
internal standard. Chemical shifts are expressed as ppm downeld
with respect to TMS.
The molecular weight of the extracted polymeric pitch was
analyzed with the 4800 Plus LDI TOF/MS Analyzer (AB Sciex) which
was equipped with 355 nm nitrogen laser and used in linear,
positive-ion mode. The samples were prepared by dissolving the
pitch in toluene. To be noted, no assistant matrix was used during
the test.
The rheological properties of the pitches were measured using a
parallel plate rheometer (Haake Mars III, Thermo Scientic, Germany) in an N2 atmosphere. The diameter of the plates was 25 mm
and data were acquired with a gap of 1.0 mm between the plates.
Before each experiment, a resting time of 10 min was applied for
temperature equilibration.
The microstructures of the cokes were observed from the polished surfaces using OLYPUMS-BX51 reected polarized light microscope. Representative images of the samples were taken using
objective of 50 magnication.

3. Results and discussion

3.1. Selection of the dehydrobromination precursor
Fig. 1 show the optimized route of preparing methylene bridged
pitch. The methyl containing aromatic hydrocarbons are reacted
with bromine molecules via a visible light irradiation assisted selective bromination method, followed by thermal dehydrobromination/polycondensation, yielding high-molecular-weight linear
pitch. Here the bromine acts as a sacricial agent for CeC bond
construction. For 1-MNP bromination, there are two possible substitution types, including ring bromination and methyl bromination. The regiochemistry of dehydrobromination/polycondensation
is usually determined by the relative value of activation energies of
the available CeBr bonds. The different CeBr bond energies in
methyl and aromatic ring are calculated using MS software (DMol3
module) based on geometry optimization process, as shown in
Table S1. Among these two types of CeBr bonds, the energy barrier
of methyl brominated 1-MNP (M-Br) transforming to methyl
radical-naphthalene (M-R) is only about half that of aromatic ring
brominated 1-MNP (A-Br) transforming to methylnaphthalene
radical (A-R) which indicates more reactivity of M-Br. After
bromine substitution reaction in methyl, the dehydrobromination
under elevated temperature could easily bridge 1-MNP molecules
into linear polymeric pitch.

Fig. 2. Photobromination scheme of 1-MNP.

3.2. Visible light irradiation assisted photobromination of 1-MNP

The aromatic ring bromination should be subjected to the
electrophilic bromination and the methyl bromination is ascribed
to free radical bromination [18]. Thus, the selective methyl substitution of Br onto 1-MNP strongly depends on the bromine radicals
originated from the homolytic cleavage of BreBr covalent bonds.
Direct heating can cleave the BreBr bonds via a collisional interconversion of kinetic energy into vibrational energy, as show in
Table S2 of the supporting materials, however the temperature
required for the complete dissociation is high than 500
C [19]
which will cause severe side reactions. Absorption of light is also
a general approach to produce radical species by intra- or intermolecular conversion of the increased electronic energy into
vibrational energy. According to Planck's equation E hc/l (E is the
energy of photons, h is Planck constant, c is light speed and l is the
wavelength of light), the photons' energy of the visible light
(400e800 nm) are calculated out in the range of 70 to 40 kcal/mol
which is theoretically sufcient to cleave BreBr bonds (46 kcal/
mol) into bromine radicals [20]. Therefore, a visible light initiator
system for selective methyl bromination of 1-MNP is employed in
this work.
After photobromination in the presence of strong visible light
(40e70 kcal/mol), four kinds of bromine-substituted products are
detected by GC/MS as illustrated in Fig. 2. The detailed product
distributions under different synthesis conditions are shown in
Table 1. It can be seen that without light irradiation, 93.9 mol% of
fraction 2 (A-Br) is generated from aromatic ring bromination while
the yield of target product fraction 3 (M-Br) is only 1.4 mol% (entry
1). While visible light irradiation is introduced to the reaction

Fig. 1. Schematic diagram for the preparation of methylene bridged pitch. (A colour version of this gure can be viewed online)

C. Ge et al. / Carbon 95 (2015) 780e788

Table 1
Products distribution of photobromination under visible light.
Entry

1
2
3
4
5
6
7
8
9

Condition

Mole percent/mol%

Smb/%

n-heptane
No solvent
CHCl3
CCl4
n-heptane
n-heptane
n-heptane
n-heptane
n-heptane

2 mol/L
e
2 mol/L
2 mol/L
2 mol/L
2 mol/L
2 mol/L
4 mol/L
1 mol/L

60
C
60
C
30
C
30
C
30
C
60
C
0
C
60
C
60
C

DK
VI
VI
VI
VI
VI
VI
VI
VI

3.8
15.9
4.8
5.0
4.6
4.9
4.1
4.1
4.6

93.9
61.4
65.9
55.7
31.3
1.4
88.7
6.6
0.5

1.4
15.3
24.9
34.7
60.5
92.8
5.2
85.9
94.5

0
0.5
0
0
0.1
0.2
0
0.4
0.3

0.9
6.9
4.4
4.6
3.5
0.7
2.0
3.0
0

1.5
19.9
27.4
38.4
65.9
98.5
5.5
92.8
99.4

Note: s: solvent kind; c: concentration of 1-MNP; T: reaction temperature; l: light

intensity (DK-dark; VI-visible light irradiation).In each entry the bromine addition is
molar equal to the 1-MNP. 1, 2, 3, 4, 5 stand for the fraction respectively in Fig. 2;
Smb: methyl bromination selectivity among products, Smb 100 3/(2 3).

system, the methyl bromination immediately became dominant.

The yield of fraction 3 can reach as high as 92.8 mol% with the
selectivity (Smb) of 98.5% (entry 6). The high yield makes it feasible
for preparing methyl bromination precursor on a large scale.
Based on the chain mechanism of photobromination [21], a
possible reaction pathway for the photobromination of 1-MNP is
proposed in Fig. 3. The bromine radical selectively reacts with
methyl group to lead chain propagation by forming methyl radicalnaphthalene. Then the chain is terminated by the recombination of
bromine atoms through molecular collision. It is found that the
reaction is strongly depending on the present of solvent. Without
using any solvent (entry 2), the methyl radical bromination is nondominant with methyl bromination selectivity Smb of only 19.9%.
The introduction of various solvent such as n-heptane, chloroform
(CHCl3) and carbon tetrachloride (CCl4) could signicantly increase
both the usage of bromine and the Smb due to a solvent effect. In
addition, the type of solvent is also an important factor to determine the Smb, here heptane is most suitable solvent compared to
CHCl3 and CCl4. As the polarity is increased in the order of n-heptane, CCl4 and CHCl3, the lowest Smb of CHCl3 may be due to the
strong polarity of the solvent which make the methyl group

783

solvated. Furthermore, the reaction temperature also plays a key

role on the target product yield and Smb. At a very low temperature
of 0
C (entry 7), aromatic ring bromination is dominated with the
Smb of only 5.5%, suggesting the light irradiation cannot produce the
bromine radicals at such low temperature. With the temperature
increasing to 30
C (entry 5), the main reaction turns into methyl
bromination and the Smb increases to 65.9%. Further increasing the
temperature to 60
C (entry 6), the yield and the Smb of the methyl
bromination can reach 92.8% and 98.5%, respectively. In addition,
the 1-MNP concentration in n-heptane also affects the Smb due to
the concentration effect. With the increase of the 1-MNP concentration, the Smb slightly decrease but still maintain a high level
(entry 8).
3.3. Dehydrobromination/polycondensation process of M-Br
After the optimization of photobromination conditions (60
C,
2 mol/L in n-heptane), a scale-up preparation (3 L) was carried out.
The obtained mixtures were further puried by a vacuum distillation through collecting the cut fraction between 115
C and 130
C
to obtain almost 100% M-Br (see Fig. S21) for thermal dehydrobromination/polycondensation process (Fig. 4(a)). The dehydrobromination of M-Br under different temperatures was analyzed by
the isothermal kinetic, based on the residual Br content calculated
from the difference by elemental CHN analysis.
The dehydrobromination kinetic curves are shown in Fig. 4(b),
and the resulting tted equations and relative parameters are
summarized in Table 2. Correlation coefcients of each curve are
over 0.99, suggesting the dehydrobromination reaction of M-Br
well conforms to a pseudo-rst-order reaction model [22]:

y M exp  kt C

(1)

where y is the residual bromine content (wt%), M is no factor coefcient, k is the reaction rate constant (min1), t is the reaction
time (min) and C is the integrating factor. The reaction rate constants increased signicantly from 1.82  103 to 0.113 with the
increase of dehydrobromination temperature. This means that high
temperature will largely shorten the polycondensation time, e.g.

Fig. 3. Mechanism scheme for the free-radical chain bromination of 1-MNP.

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C. Ge et al. / Carbon 95 (2015) 780e788

Fig. 4. Dehydrobromination/polycondensation curves of M-Br under different temperatures. (a) Scheme of dehydrobromination/polycondensation; (b) Isothermal dehydrobromination kinetic curves; (c) Arrhenius plots of lnk and 1/T for the thermal dehydrobromination of M-Br. (A colour version of this gure can be viewed online)

Table 2
Fitted results of the dehydrobromination curves.
Debromination temperature
200
230
250
270
a
b
c
d

C
C


C


C

Fitted equationa
y
y
y
y

27.81exp(t/549.29) 0.56
25.59exp(t/45.79) 2.35
23.16exp(t/27.34) 1.58
6.83exp(t/8.84) 2.14

R2b

nc

kd/min1

0.997
0.995
0.996
0.992

1
1
1
1

1.82  103
2.18  102
3.66  102
0.113

y and t stand for the residual bromine content (wt%) and holding time (min) respectively.
Correlation coefcient.
Dehydrobromination reaction order.
Reaction rate constant.

only 30 min for 270
C. According to the Arrhenius equation [23]:

ln k Ea =RT C

(2)

the apparent activation energy Ea for the thermal dehydrobromination of M-Br can be calculated. By ploting lnk to 1/T in Fig. 4(c),
the Ea for the thermal dehydrobromination is calculated as 122.6 kJ/
mol from the slope value.

3.4. Characterization of the polymeric pitches

Table 3
Structural parameters calculated from 1H NMR spectra.
Pitch

T200
T230
T250
T270
a
b
c

Isotropic pitches are prepared using methyl substituted intermediates at different dehydrobromination temperatures. After
n-hexane extraction, the high-softening-point pitches are obtained.
Some physical properties including softening point, solubility and
H/C ratios of the extracted pitches are summarized in Table 3. The
softening points are in the range of 196e250
C, increasing with the
dehydrobromination temperature. The high value of the H/C ratio
(0.67e0.61) should be noted because conventionally prepared
high-softening-point pitches subjected to thermal steps show

S.P.a
(
C)

TSb
(wt%)

Ultimate analysis

C
(wt%)

H
(wt%)

H/C

196
210
218
250

100
100
100
100

92.61
93.01
93.13
93.56

5.14
4.91
4.79
4.78

0.67
0.63
0.62
0.61

H NMR

Har

Ha

HCH2

Hb

Hg

fad

0.84
0.86
0.87
0.89

0.16
0.14
0.13
0.11

0.12
0.10
0.09
0.07

0
0
0
0

0
0
0
0

0.89
0.90
0.91
0.92

Softening point.
Toluene soluble fraction.
Atomic ratio.
Aromaticity [26].

values of ca. 0.51e0.55 [24,25]. Moreover, the perfect solubility

(100%) in toluene of these pitches lays over anything else of typical
high-softening-point pitches derived from petroleum and coal
residues. All these physical properties hint the unique molecular
structure of the as-synthesized pitches.
The hydrogen distributions of these pitches are analyzed by 1H

C. Ge et al. / Carbon 95 (2015) 780e788

785

Fig. 5. 1H NMR spectra of the extracted pitches. (A colour version of this gure can be viewed online)

NMR spectra, as shown in Fig. 5. 1H NMR spectra shows chemical

shift of aromatic hydrogens (Har) in the region 6.0e9.0 ppm. The
chemical shift of aliphatic hydrogens (Hal) in the region
0.5e5.2 ppm is subdivided into a hydrogens (Ha) in the region
2.0e5.2 ppm, b hydrogens (Hb) in the region 1.0e2.0 ppm, g hydrogens (Hg) in the region 0.5e1.0 ppm respectively [27,28]. More
specically, the hydrogens in ring-joining methylene or methane
which belong to Ha are assigned as HCH2 in the chemical shift range
of 5.2e4.0 ppm. The distribution of all the hydrogens are determined by digital integration of Har and Hal (Ha, Hb and Hg) band
intensities normalized over the complete spectrum. For comparison, pulse delay time of 1 s and 10 s are adopted respectively during
the recording of T270. However, the results shown in Fig. S24 and
Table S3 indicate an independent relationship of the hydrogen
signals with the extended pulse delay time. Thus a pulse delay time
of 1 s is used for all the samples and the integration results are
summarized in Table 3. It can be found that there is no evident
signal of Hb and Hg, which indicates that most of the methyl side
chains are reserved and attached as a-groups to the aromatic rings.
Among the a-groups, about 75% (T200) to 64% (T270) of the Ha
hydrogens are detected in the position of methylene which indicates that most of the a-groups are transformed into bridges for
the linkage of aromatic rings. This result provides solid evidence
that the prepared pitches mainly consist of the methylene bridged
structure. With assistant of ACD/HNMR (version 6.12) predictor
software [29], the chemical shift of 1-MNP based model oligomers
can be calculated and is shown in Fig. S25. Such results of the
predicted 1H NMR spectrums could provide powerful support for
the denition of bonding position of the oligomers in this pitch. By
comparing the authentic spectra with the predicted ones, the pitch
oligomers exhibit major aliphatic peaks at ca. 5 ppm and 2.7 ppm,
which strongly suggested a majority of oligomers in 1, 4 or 1, 5
connections in the alpha-position of the naphthalene rings. However, a small amount of broadening area is also observed right to
the principle ones, which should be assigned to some other
bonding linkages, most possibly belong to beta-position connection
in the naphthalene rings. By the judgment of local variations of the
methyl chemical shift in Fig. S26, we can furtherly suggest a linear
structure of the major fraction in the pitch. The hydrogen distributions of the pitches also show that Har content increases and Hal
content decreases with the dehydrobromination temperatures.

This should be due to the enhanced polycondensation at elevated

temperature, which results in the interlinkage of more adjacent
naphthalene rings by methylenes. In addition, the aromaticity (fa)
increases gradually with the temperature increasing, suggest the
pitches prepared at higher temperature exhibit more condensed
polynuclear structures.
The average molecular weight and molecular weight distribution of the pitches are important structural parameters that
determine their properties. The molecular weight distributions of
these pitches are analyzed by laser desorption/ionization time-ofight mass spectroscopy (LDI-TOF/MS) as shown in Fig. 6(a). All
the pitches consist of very sharp peaks that response to various
oligomers and major in the type of tetramer and pentamer. For
pitch polycondensed at 200
C, its molecular weight distribution is
in the narrow range of 420e983 with an average molecular weight
of 781.7. Increasing the temperature could obviously increase molecular weight of the pitch and cause the formation of high order
oligomers. Even oligomer having eighteen subunits (2538 m/z) can
be obtained for pitch polycondensed at 270
C. Despite relatively
high average molecular weight of 1500, the pitch is still 100% soluble in toluene, possibly due to their unique linear structure. In
addition, most of the oligomers in each of the pitch were suggested
to lose some hydrogens or even methylene (methyl) as a group of
peaks were found left to the ideal ones, as indicated by Fig. 6(b). The
extent of the molecular evolution seems to be more serious for the
pitches prepared at a higher temperature. Such molecular rearrangement may also lead to the decrease of C/H ratio as compared
to the ideal oligomers. Based on the results of elemental analysis, 1H
NMR and LDI-TOF/MS, some possible molecules in the pitches are
illustrated in Fig. 6(c), which describes ideal oligomers with a
similar linear structure containing repeat subunits.
3.5. Rheological behavior of the polymeric pitches
The as-prepared pitches exhibit some typical features of polymers, i.e. large molecular weight and linear structure with repeated
subunits. The physical properties of the pitches are strongly
dependent on the number of the subunit. As subunit number is
increased, softening point temperatures increase quickly. In order
to further gain fundamental understanding of the processing ability
of such materials, the rheological properties that govern the ow

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C. Ge et al. / Carbon 95 (2015) 780e788

Fig. 6. LDI-TOF/MS spectrums for the as-prepared pitches. (a) Whole spectrum for each pitch; (b) Spectrum for the variation of representative tetramers in each pitch; (c) Possible
structures for the oligomers. (A colour version of this gure can be viewed online)

Fig. 7. Rheological behavior of the extracted polymeric pitches. (a) Apparent viscosity vs. temperature curves of T230 and T270; (b) Apparent viscosity vs. shear rate curves under
different temperatures for T230 and T270. (A colour version of this gure can be viewed online)

behavior when the pitches are processed in the molten state are
studied by using HAAKE Rotational Rheometer. Fig. 7(a) shows the
apparent viscosity versus temperature curves of pitches polycondensed at the temperatures of 230 and 270
C (named T230 and
T270, respectively). The apparent viscosity of both samples significantly decreases with the temperature increasing, even being less
than 10 Pa s at the temperature of 340
C. Such high sensitive
viscosity to temperature should be due to the exible methylene
chain in the pitch that facilitates thermal movements of the linear
molecules. In addition, low viscosity at temperatures near the
softening point make it suitable precursor for carbon ber preparation, making the spinning process more stable and avoiding
bubble formation.
The shear rheology, which is useful information for ber spinning, is also measured by ranging the shear rate at constant temperature to assess the ow behavior of the molten pitches. Fig. 7(b)
shows the apparent viscosity/shear rate curves of sample T230 at
250
C and T270 at 250
C, 260
C and 270
C, respectively. For all
the tests, regardless of the testing temperature, the curves show
very similar change of the apparent viscosity with shear rate
increasing. At low shear rates, a usual pattern of shear-thinning
behavior is observed following a common Newtonian plateau for
very small shear rates. However, an interesting phenomenon of
shear-thickening behavior is achieved as the shear rate continues to
increase above a critical value of ca. 20 s1. While at high shear

rates, a local maximum of the viscosity (weak plateau) is obtained

in the range of 100e300 s1 and then a subsequent shear-thinning
region occurs again at extremely high shear rates. Such behavior of

Fig. 8. Coke yield of pitch T200 and T270 under 550
C for 2 h with different
carbonization pressures. (A colour version of this gure can be viewed online)

C. Ge et al. / Carbon 95 (2015) 780e788

787

Fig. 9. Optical microphotographs of cokes obtained from pitch T200 under (a) atmospheric pressure, (b) 1.1 MPa, (c) 3.1 MPa and from pitch T270 under (d) atmospheric pressure,
(e) 1.1 MPa and (f) 3.1 MPa. (A colour version of this gure can be viewed online)

these molten linear polymeric pitches is similar to that of conventional linear polymers in solution [30,31]. These results suggest
that shear rate is an important external variable that can tailor the
viscoelastic properties of the pitches for practical processing.
3.6. Carbonization properties of the polymeric pitches
The coke yield and properties were important aspects for the
evaluation of further application of polymeric pitches [16]. Thus,
the carbonization behaviors of the as-prepared pitches were
investigated at 550
C for 2 h under atmospheric pressure, 1.1 MPa
and 3.1 MPa respectively. Here, pitch T200 and T270 were used as
the precursors for comparison. The coke yields of the two pitches
were illustrated in Fig. 8. It can be found that the coke yield of T270
was markedly higher than that of T200 at the atmospheric pressure. The yield of pitch T270 was 51% while the yield was only 34%
for pitch T200. Such signicant difference in the coke yield should
be caused by the competition between condensation and pyrolysis
reaction of the pitches which mainly depended on polycondensation degree and the size of the repeated aromatic units.
Moreover, the coke yield of both pitches increased gradually with
the increasing pressure, as the coke yield was 39.3% and 57.4%
under 3.1 MPa for pitch T200 and T270 respectively.
The optical micrographs of the cokes obtained at 550
C for 2 h
under different carbonization pressure were shown in Fig. 9. The
coke produced from pitch T200 under atmospheric pressure
exhibited anisotropic ow domains. The formation of mesophase
(composed of disc-like molecules [32]) during the carbonization
suggested that methylene groups were incorporated into aromatic
rings by dehydrogenation [33,34], leading to a larger aromatic ring
size which favors the formation of plane molecules. With the
increasing of carbonization pressure, the optical texture of the cokes
obtained from pitch T200 were improved in both of the size and
uniformity of anisotropic units. However, the coke produced from
pitch T270 show a ne isotropic texture under atmospheric pressure, and no anisotropic phase is developed even under the pressure of 3.1 MPa. As pitch T200 and T270 exhibit similar molecular
structure, the distribution of molecular length (as well as molecular
weights) is quite critical for the mesophase formation. In fact, with
the increase of molecular length, molecular deformation is more
likely to occur during the carbonization, leading to a large conformational entropy change needed for achieving the parallel molecular orientation [35]. Thus severer conditions might be essential for
the mesophase developing from this long molecular pitch.

4. Conclusions
Highly linear methylene-bridged pitches are prepared from 1methylnaphthalene using bromine as a sacricial agent for CeC
bond construction. The lower value of calculated methylic CeBr
bond energy as compared to that of aromatic CeBr provides a direct
basis for the determination of adopting methyl bromination reaction route. The key to the synthesis relies on a visible light irradiation induced free-radical bromination, which could produce the
methyl brominated 1-methylnaphthalene with high yield and high
selectivity. After a dehydrobromination/polycondensation process,
polymeric pitches with a high-softening-point are obtained. The
isothermal kinetic study reveals the dehydrobromination reaction
follows a pseudo-rst-order reaction model with apparent reaction
activation energy of 122.6 kJ/mol. The as-synthesized pitches are
composed of unique linear chain with repeated subunits. They
exhibit excellent physical properties such as high purity, high
aromaticity, 100% soluble in toluene and very low viscosity. The
coke yield of such pitches at 550
C can reach as high as 57%. Optical
micrographs show that the coke obtained from short molecular
pitch thoroughly show anisotropic textures of ow domains while
the coke from long molecular pitch mainly exhibit ne isotropic
textures.
Acknowledgments
The nance and encouragement of this work is supported by
National Natural Science Foundation of China (U1303291 and No.
51272077).
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.carbon.2015.09.003.
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