Synthesis of comb polyphenylenes by Suzuki coupling from AB macromonomers

Article abstract of DOI:10.1002/pola.27167

A series of soluble comb polyphenylenes (PPs) were synthesized by Suzuki coupling polycondensation from AB macromonomers. After post-polymerization treatment, the comb PPs have a good symmetric single-peak shape in the GPC curves with reasonable polydispersity indexes ranging from 1.15 to 1.74. Copyright

Full text of DOI:10.1002/pola.27167

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Synthesis of Comb Polyphenylenes by Suzuki Coupling from AB
Macromonomers
Sheng Zhou, Yu Zhou, Haijian Tian, Yufeng Zhu, Yu Pan, Feng Zhou, Qikai Zhang,
Zhihao Shen, Xinghe Fan
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education,
College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
Correspondence to: X. Fan (E-mail: fanxh@pku.edu.cn) or Z. Shen (E-mail: zshen@pku.edu.cn)
Received 17 November 2013; accepted 11 March 2014; published online 25 March 2014
DOI: 10.1002/pola.27167
KEYWORDS: ATRP; conjugated polymer; graft copolymer; macromonomers
presence of Pd(PPh3)4.28,29 Compared to radical polymeriza-
tion of macromonomers, Suzuki coupling polycondensation
INTRODUCTION Comb polymers, densely grafted polymer
brushes, have been widely studied in recent years.1–5 They
using AB macromonomers effectively decreases the influence
of the concentrations of macromonomers.2 Suzuki coupling
also has the advantage of a mild reaction condition and can
be easily controlled compared to other methods such as
atom transfer radical polymerization (ATRP),30 anionic poly-
merization,31 and ring-opening polymerization32 for the
preparation of comb polymers. However, polycondensation
methods usually give polymers with a broader molecular
weight distribution than living radical polymerizations.33
have various branching topologies because of the differences
in grafting densities and side-chain lengths. Such differences
bring in many new conformations and properties. Comb
polymers have already worked in nature with particular
functions such as proteoglycans6 which clean lung airways.7,8
Inspired by the proteoglycans, researchers are now prepar-
ing comb polymers with functional groups or side chains.9,10
Many works in drug-delivery carriers,11 molecular pressure
sensors,12 and solid optical materials13 have been reported.
Three synthetic strategies for preparing comb polymers are
usually used, that is, “grafting to,”14,15 “grafting from,”16,17
and “grafting through.”18–20 Among them, “grafting through”
is the only way to prepare comb polymers with 100% graft-
ing density and side chains having the same length.
Herein, we describe the synthesis of soluble comb PPs by
Suzuki polycondensation from polystyrene (PS)-based AB
macromonomers. In such a reaction, it is not necessary to
control the feeding ratio compared to the reaction of an A
monomer with a B monomer. Comb polymers prepared by
Suzuki coupling can have the highest grafting density and
side chains with the same length. The resulting PPs, possi-
bly soluble in most organic solvents, may still have excel-
lent mechanical properties, thermo-oxidative stability, and
optoelectric properties. Moreover, the most attracting part
is that comb polymers obtained using this method exhibit a
symmetric single peak in the gel permeation chromatogra-
phy (GPC) curves with reasonable polydispersity indexes
ranging from 1.15 to 1.74. PS is used as a model side chain
in this work to establish this new method for preparing
comb polymers by Suzuki coupling polycondensation. Con-
sidering the potential application of PPs, we may prepare
comb PPs with functional side chains, for example, hydro-
philic, pH-responsive, or thermo-responsive side chains, in
the future. Suzuki coupling polycondensation may be an
effective method to prepare comb polymers with specific
structures and properties.
Comb polymers may be applied as optical materials to solve
the energy problem, which is one of the most important
challenges we are facing.21 Polyphenylenes (PPs) are impor-
tant compounds that can be used in organic electronic appli-
cations.22 PP is a kind of conjugated polymer with excellent
mechanical properties, thermo-oxidative stability, and good
optoelectric properties. It has been used in solar cells23 and
transistors.24 Unfortunately, PP is insoluble in many organic
solvents, which limits its preparation and application. The
poor solubility also makes it difficult to prepare PPs with
large molecular weights. In order to improve the solubility
of PP, pendant alkyl side chains have been attached to the
PP backbones,25,26 and PPs grafted with polymers have also
been reported.27 Yagaci and coworkers prepared PP graft
copolymers by reacting a monobromo monomer (A) with a
monoboronic-ester monomer (B) via Suzuki coupling in the
Additional Supporting Information may be found in the online version of this article.
C
V
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EXPERIMENTAL
product was purified by passing through a silica gel column
using dichloromethane/acetone (3:1, vol:vol) as the eluent.
Yield: 22%. The crude product (0.940 g, 3.20 mmol) was put
into a flask, and then pinacol (0.830 g, 7.00 mmol) and 50.0
mL of dichloromethane were added. After the solution was
refluxed for 24 h, the mixture was washed with water, dried,
and purified by flash chromatography using dichlorome-
thane/petroleum ether (1:1, vol:vol). Yield: 88%. For 2: 1H
NMR (CDCl3, d, ppm): 1.36 (s, 12H), 2.23 (s, 3H), 7.0727.09
(d, 1H), 7.2927.31 (d, 2H), 7 .3527.37 (d, 1H), 7.42 (s, 1H),
7.8527.87 (d, 2H).
Materials
Benzoyl peroxide (BPO, CP, recrystallized from methanol and
chloroform), CuBr (washed by glacial acetic acid and then by
methanol, and dried), styrene (AR, Beijing Chemical
Reagents, used after distillation), and tetrahydrofuran (THF,
AR, Beijing Chemical Reagents, used after distillation) were
subjected to pre-treatment before use. 5-Bromo-2-
iodotoluene (98%, Acros), 4-bromophenylboronic acid (98%,
J&K), Pd(PPh3)4 (J&K), n-BuLi (2.4 M solution in hexane,
Acros), pinacol (99%, J&K), N,N,N0,N0,N00-pentamethyldiethyle-
netriamine (PMDETA, 98%, TCI), and other reagents pur-
chased from Beijing Chemical Reagents were directly used.
Synthesis of Initiators
Compound 2 (0.730 g, 1.96 mmol), N-bromosuccinimide
(NBS, 0.400 g, 2.20 mmol), and BPO (0.0160 g, 0.0700
mmol) were added into a flask, and 60.0 mL of CCl4 was
added. The solution was slowly heated to 80 ꢀC and stirred
for 5 h under reflux. The mixture was filtered to remove suc-
cinimide and washed with CH2Cl2 and water, dried over
Na2SO4, and finally purified by passing through a silica gel
column using dichloromethane/petroleum ether (1:1, vol:vol)
as the eluent. Yield: 46%. For 4: 1H NMR (CDCl3, d, ppm):
1.37 (s, 12H), 4.35 (s, 2H), 7.1127.13 (d, 1H), 7.3227.35 (d,
1H), 7.4027.42 (d, 2H), 7.67 (s, 1H), 7.8827.90 (d, 2H). MS
(EI) m/z (%): 452 (M1, 40), 437 (5), 371 (34), 292 (base).
Characterization Methods
1H NMR spectra were recorded at 400 MHz on a Bruker ARX
400 spectrometer. Mass spectra were recorded on
a
Finnigan-MAT ZAB-HS. GPC measurements were performed
on a Waters 2410 instrument consisting of a Waters 2410
refractive index (RI) detector, and three Waters m-Styragel
columns (103, 104, and 105 Å) were used. THF was used as
eluent at a rate of 1 mL/min. Polystyrenes were used as
standards. GPC-multi-angle laser light scattering (GPC-
MALLS) experiments were also performed on a Waters
instrument equipped with a Wyatt DAWN HELEOS 18-angle
laser light scattering detector (k 5 658 nm). The scattering
angle ranges from 15ꢀ to 165ꢀ. Polystyrenes were used as
standards, and dn/dc was 0.185. Thermogravimetric analysis
(TGA) was conducted on a TA Q600 SDT instrument in a
nitrogen atmosphere. Differential scanning calorimetry (DSC)
was performed on a Mettler-Toledo DSC 1 under nitrogen.
UV–vis spectra were recorded on a PE Lambda 35. Fluores-
cence spectra were recorded on a F-7000 fluorescence spec-
trophotometer using THF solutions at ambient temperature.
Preparation of PS Macromonomers
Styrene (6.8 mL, 59 mmol), PMDETA (137 mL, 0.660 mmol),
initiators (0.297 g in 1.0 mL chlorobenzene, 0.660 mmol),
additional 7.0 mL of chlorobenzene, and CuBr (95 mg, 0.66
mmol) were charged into a polymerization tube. Three
freeze-pump-thaw cycles were performed. The tube was
stirred at 90 ꢀC in an oil bath for 18 h. The mixture was
then diluted with THF and passed through a neutral alumina
column to remove the copper complex. The product was pre-
cipitated out with methanol, and the solid was collected after
filtration and dried at 35 ꢀC in a vacuum oven overnight.
With GPC, molecular weight (Mn,GPC) and polydispersity
index (PDI) were obtained. A mixture of macromonomers
coded PS1 was prepared, with Mn,GPC 5 7800 g/mol and PDI
5 1.08. Yield: 34%. For PS1: 1H NMR (CDCl3, d, ppm):
1.2621.53 (m, OA(CH3)2A(CH3)2AO, aliphatic CH2 of PS),
1.8522.05 (m, ArACH2, aliphatic CH of PS), 6.3526.58 (m,
aromatic of PS), 6.9427.09 (d, aromatics of PS and PP back-
bone). A second mixture of macromonomers coded PS2 was
also prepared using the same method, with Mn,GPC 5 19,100
g/mol and PDI 5 1.24.
Synthesis of 4,40-Dibromo-2-methyl-biphenyl (1)
4-Bromophenylboronic acid (9.60 g, 48.0 mmol), K2CO3
(7.11 g, 50.0 mmol), and Pd(PPh3)4 (1.66 g, 1.40 mmol)
were added into a three-necked flask which was vacuumed
and purged with nitrogen. Then 5-bromo-2-iodotoluene (7.0
mL, 50 mmol) and CH3CN/H2O (240 mL, 3:1) were added
sequentially under nitrogen. The solution was stirred for 24
h at 90 ꢀC before the reaction was quenched with 1 M HCl.
The reaction mixture was washed by water, extracted with
CH2Cl2, and dried over Na2SO4. The final product was passed
through a silica gel column using petroleum ether as the elu-
1
ent. Yield: 40%. For 1: H NMR (CDCl3, d, ppm): 2.22 (s, 3H),
7.0427.05 (d, 1H), 7.1427.15 (d, 2H), 7.3527.37 (d, 1H),
7.42 (s, 1H), 7.5327.55 (d, 2H).
Preparation of Comb PPs
PS1 (0.600 g, 0.0800 mmol), Pd(PPh3)4 (13.0 mg, 0.0100
mmol), NaHCO3 (4.0 mL, 0.1 M), and 16.0 mL of THF weꢀre
charged into three Schlenk tubes, which were stirred at 70 C
for 1 day, 2 days, and 3 days, respectively. The solutions were
quenched with 1 M HCl, and products were precipitated out
with methanol. And solids were collected after filtration and
dried. Three comb PPs based on PS1 were prepared: PS1PP1
(polymerized for 1 day, Mn,GPC 5 28,800 g/mol, PDI 5 1.15),
PS1PP2 (polymerized for 2 days, Mn,GPC 5 69,500 g/mol, PDI
Synthesis of 40-Bromo-2-methyl-biphenyl-4-yl-boronic
Acid Pinacol Diester (2)
Compound 1 (4.73 g, 15.0 mmol) was added to THF (70.0
ꢀ
mL) and stirred. The solution was cooled to 278 C, and n-
BuLi (6.4 mL, 15 mmol) was slowly added. The mixture was
stirred at the same temperature for 1 h, and B(OCH3)3 was
then slowly added. The solution was further stirred for 18 h.
After being washed with water and dried over Na2SO4, the
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SCHEME 1 Synthetic route of PS macromonomers.
5 1.74), and PS1PP3 (polymerized for 3 days, Mn,GPC
5
influence the ATRP process, and the two initiators almost
have the same reactivity. Finally, comb PPs were obtained by
Suzuki coupling polycondensation from the PS macromono-
mers PS1 and PS2. The GPC traces of the comb PPs are
shown in Figure 1 and Supporting Information Figure S5 as
well. The structures of the intermediates were confirmed by
1H NMR spectra. And those of the initiators were also con-
1
108,100 g/mol, PDI 5 1.67). For PS1PP3: H NMR (CDCl3, d,
ppm): 1.2621.53 (m, aliphatic CH2 of PS), 1.8622.07 (m,
ArACH2, aliphatic CH of PS), 6.3526.57 (m, aromatic of PS),
7.0427.08 (d, aromatics of PS and PP backbone). PS2 was also
used to prepare comb PPs using the same method.
1
firmed by mass spectra. H NMR spectra of PS1 and PS1PP3
are presented in Figure 2.
RESULTS AND DISCUSSION
Synthesis of Comb Polymers
The resonance peak at l0 corresponding to the boronic ester
protons nearly disappears after the final Suzuki coupling.
Comb PPs with different molecular weights were obtained
by many times of precipitation.
The overall strategies are presented in Schemes 1 and 2. First,
compound 1 was prepared by Suzuki coupling. Then the boric
acid ester 2 was synthesized by using n-BuLi, followed by the
reaction with trimethylborate at 278 ꢀC, and finally reacted
with pinacol in CH2Cl2. The boric acid ester was used because
of its higher solubility in CCl4 than that of the boric acid. The
ATRP initiator was obtained by bromination of 2 with NBS.
Note that, beginning from the synthesis of the boric acid, the
OH group may appear at either side of the biphenyl unit.
Because these two isomers have almost the same polarity,
they cannot be separated. Thus, the initiator is a mixture of
two compounds of 4 and 5 with the boric acid ester group at
different sides. The molar ratio of 4 to 5 is 2:1, as shown in the
1H NMR result (Supporting Information Fig. S3).
Determination of Molecular Weights
As shown in Table 1, firstly, the number-average molecular
weights (Mns), weight-average molecular weights (Mws), and
Next, the PS macromonomers were prepared by ATRP from
the initiators 4 and 5. The macromonomers show a symmet-
ric single-peak shape in GPC traces (Fig. 1 and Supporting
Information Fig. S5), rather than two peaks. This indicates
that the mixture of initiators 4 and 5 did not strongly
FIGURE 1 GPC traces of PS1 and comb PPs prepared from
PS1. [Color figure can be viewed in the online issue, which is
available at wileyonlinelibrary.com.]
SCHEME 2 Synthesis of comb PPs by Suzuki coupling
reaction.
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FIGURE 3 TGA curves of comb PPs prepared from PS1 at a
heating rate of 10 ꢀC/min under nitrogen. [Color figure can be
viewed in the online issue, which is available at
wileyonlinelibrary.com.]
FIGURE 2 1H NMR spectra of PS1 and PS1PP3. [Color figure
can be viewed in the online issue, which is available at
wileyonlinelibrary.com.]
Thermal Properties
PDIs of PS and comb PPs were measured by GPC equipped
with an RI detector. As shown in Table 1, the Mn values of
PS1, PS1PP1, PS1PP2, and PS1PP3 were 0.078 3 105, 0.29
3 105, 0.70 3 105, and 1.08 3 105 g/mol, respectively. Reg-
ular GPC experiments can only give a general tendency of
molecular weights. These values are not accurate for comb
polymers because molecular weights obtained from GPC are
based on linear PS standards, and comb polymers are not
linear. Usually molecular weights of comb polymers esti-
mated by GPC are smaller.34 Therefore, GPC-MALLS experi-
ments were conducted to obtain reliable molecular weights.
Degrees of polymerization (DPs, Mn of comb PP divided by
Mn of PS macromonomer) were estimated using GPC-MALLS
data. As shown in Table 1, the molecular weights of comb
PPs measured by GPC-MALLS experiments are clearly larger
than those by regular GPC.
Thermal properties of the comb PPs were studied by TGA
(Fig. 3) and DSC (Fig. 4) experiments, with data shown in
Table 1. The comb PPs have excellent thermal stabilities.
Temperatures at which 5% weight loss occurs (Td) of
PS1PP1, PS1PP2, and PS1PP3 are 344, 358, and 362 ꢀC,
respectively. Td increases with increasing DP of the comb PP.
For comb PPs with the same length of PS side chains, the
polymer with a larger molecular weight probably has a lon-
ger conjugated structure and thus is more stable. Figure 4
shows the DSC thermograms of comb PPs prepared from
PS1 during the second heating. Apparently, each comb PP
exhibits the Tg of the PS side chain. The Tg values of PS1PP1,
PS1PP2, and PS1PP3 are 97, 99, and 101 ꢀC, respectively,
which are almost the same. TGA and DSC results of comb
PPs prepared from PS2 are shown in Supporting Information
Figures S6 and S7.
TABLE 1 Molecular Characteristics and Thermal Properties of PS and Comb Polymers
Mn,GPC
(3105 g/mol)
Mw,MALLS
(3105 g/mol)
PDIa
PDIb
DPb
c
Td (ꢀC)
d
Tg (ꢀC)
Polymer
PS1
0.078
0.29
0.70
1.08
0.19
0.39
0.86
1.16
1.08
1.15
1.74
1.67
1.24
1.29
1.60
1.64
–
–
–
–
–
PS1PP1
PS1PP2
PS1PP3
PS2
0.35
1.75
2.28
–
1.08
1.25
1.02
–
4
344
358
362
–
97
99
101
–
18
29
–
PS2PP1
PS2PP2
PS2PP3
0.48
1.17
1.67
1.14
1.10
1.03
2
347
368
375
94
98
102
6
8
a
d
Obtained from GPC experiments.
Obtained from DSC experiments during heating at rate of 10 ꢀC/min in
b
c
Obtained from GPC-MALLS experiments.
Obtained from TGA experiments at a heating rate of 10 ꢀC/min in
nitrogen.
nitrogen.
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FIGURE 5 UV–vis spectra of PS1, PS1PP1, PS2PP2, and the PP
backbone polymer in THF. The DPs of PS1PP1 and PS2PP2 are
nearly the same. [Color figure can be viewed in the online
issue, which is available at wileyonlinelibrary.com.]
FIGURE 4 DSC thermograms of comb PPs prepared from PS1
during the second heating at a rate of 10 ꢀC/min. [Color figure
can be viewed in the online issue, which is available at
wileyonlinelibrary.com.]
Photophysical Properties
PP backbone polymer, and the shift of PS2PP2 is larger than
that of PS1PP1. This is probably also caused by the longer
PS side chains in PS2PP2 which has a shorter conjugation
length, in accordance with the UV–vis results.
UV–vis and fluorescence spectra were used to investigate the
photophysical properties of the comb PPs. For comparison, a
PP backbone polymer without PS side chains was prepared
(Scheme 3, Mn,GPC 5 2400 g/mol, PDI 5 1.28). The PP back-
bone polymer is insoluble in most organic solvents including
N,N-dimethylformamide, CH2Cl2, CHCl3, and toluene and can-
not be purified by reprecipitation. It is only partly soluble in
THF. Therefore, the comb PPs have better solubilities over
the PP backbone polymer due to the substitution of long
side chains. UV–vis spectra of PS1, PS1PP1, PS2PP2, and the
PP backbone polymer are shown in Figure 5. The PS chain
shows a kmax of around 260 nm, while the PP backbone
polymer shows a kmax of about 300 nm. And UV–vis spectra
of the comb PPs are basically the summation of those of PS
and the PP backbone polymer. For example, absorption of
the comb PPs at around 300 nm comes from the PP back-
bone. PS1PP1 and PS2PP2 have nearly the same DPs and are
used to make a comparison. The absorption peak of PS2PP2
around 300 nm is weaker than that of PS1PP1, possibly
because the longer side chains disrupt the conjugation and
absorption of the backbone more severely.
CONCLUSIONS
A series of new soluble comb PPs with different lengths of
backbones and PS side chains were successfully prepared by
Suzuki coupling polycondensation. Combining with ATRP and
Suzuki coupling via a “grafting through” strategy, the comb
PPs were prepared with high grafting densities and con-
trolled lengths of PS side chains. The comb PPs prepared in
this work have a rather symmetric single peak in the GPC
curves with a reasonable PDI in the range 1.15–1.74. The
The fluorescent properties of PS1, PS1PP1, PS2PP2, and the
PP backbone polymer were also investigated, with the
results shown in Figure 6. PS is not fluorescent and not
included in the figure. The PP backbone polymer and the
comb PPs show a maximum emission peak at around 370
nm. The peak blue shifts for the comb PPs compared to the
FIGURE 6 Fluorescence spectra of PS1, PS1PP1, PS2PP2, and
the PP backbone polymer in THF. [Color figure can be viewed
in the online issue, which is available at wileyonlinelibrary.
com.]
SCHEME 3 Synthesis of the PP backbone polymer without PS
side chains.
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15 H. Gao, K. Matyjaszewski, J. Am. Chem. Soc. 2007, 129,
6633–6639.
comb PPs have excellent thermal stabilities. Owing to their
conjugated structures, these comb PPs may be useful in
optoelectric applications.
16 S. De Smet, S. Lingier, F. Du Prez, Polym. Chem. 2014,
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17 K. Ishizu, H. Yamada, Macromolecules 2007, 40, 3056–3061.
ACKNOWLEDGMENT
18 S. L. Pesek, X. Li, B. Hammouda, K. Hong, R. Verduzco,
Macromolecules 2013, 46, 6998–7005.
This research was supported by the National Natural Science
Foundation of China (Grants 21174006 and 21134001).
19 A. Cappelli, M. Paolino, G. Grisci, G. Giuliani, A. Donati, R.
Mendichi, A. C. Boccia, F. Samperi, S. Battiato, E. Paccagnini,
E. Giacomello, V. Sorrentino, M. Licciardi, G. Giammona, S.
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