Functional mesoporous poly (ionic liquid) derived from P123: From synthesis to catalysis and alkylation of styrene and o-xylene

Article abstract of DOI:10.1002/aoc.4719

A novel strategy was proposed for the fabrication of high-performance acidic mesoporous poly ionic liquids catalyst. In this work, mesoporous poly ionic liquids (MPILs) were synthesized with P123 (PEO₂₀PPO₇₀PEO₂₀) served a

Full text of DOI:10.1002/aoc.4719

Received: 12 July 2018
DOI: 10.1002/aoc.4719
Revised: 22 October 2018
Accepted: 29 October 2018
F U L L P A P E R
Functional mesoporous poly (ionic liquid) derived from
P123: From synthesis to catalysis and alkylation of styrene
and o‐xylene
Beibei Wang
Chao Zhang
| Xiaoli Sheng | Yuming Zhou | Zhiying Zhu | Yonghui Liu | Xiao Sha |
| Huaying Gao
School of Chemistry and Chemical
Engineering, Southeast University,
Jiangsu Optoelectronic Functional
Materials and Engineering Laboratory,
Nanjing 211189, People's Republic of
China
A novel strategy was proposed for the fabrication of high‐performance acidic
mesoporous poly ionic liquids catalyst. In this work, mesoporous poly ionic
liquids (MPILs) were synthesized with P123 (PEO PPO PEO ) served as
20
70
20
3
−
pore‐forming agent. Then, MPILs were treated with PW anion exchange,
thereby fabricating PW/MPIL‐S(x). MPIL and PW/MPIL‐S(x) were character-
ized by scanning electron microscope (SEM), transmission electron microscopy
(TEM), Thermogravimetric analysis (TA), N2 adsorption–desorption and
Fourier transform infrared (FT‐IR) spectra and X‐ray photoelectron spectros-
copy (XPS) spectra. The effect of solvent and concentration of P123 on the
morphology and mesoporous structure of MPILs were investigated systemati-
cally. And the results show that MPILs were featured with mesoporous
Correspondence
Xiaoli Sheng and Yuming Zhou, Huaying
Gao School of Chemistry and Chemical
Engineering, Southeast University,
Jiangsu Optoelectronic Functional
Materials and Engineering Laboratory,
Nanjing 211189, People's Republic of
China.
Email: xlsheng@seu.edu.cn;
ymzhou@seu.edu.cn
2
channel structure, high surface area (up to 737 m /g) and large pore volumes
3
(
1.16 cm /g), which benefit heterogeneous phase reaction (such as, alkylation
Funding information
of styrene with o‐xylene). In the alkylation reaction, under optimal reaction
conditions, the catalyst PW/MPIL‐THF (4.0 g) shows high conversion of
styrene (100%) and PXE yield (96.21%), demonstrating the excellent catalytic
activities. Furthermore, PW/MPIL‐S(x) are easy to be separated from the
catalytic system by filtration and show no obvious decrease in catalytic activity
after 6 cycle runs. The obtained PW/MPIL‐S(x) catalyst exhibit high thermal
and mechanical stability as well, indicating extensive application in high
temperature acidic catalysis. This work might open up a new method for the
synthesizing of porous polymer catalysts in the future.
Priority Academic Program Development
of Jiangsu Higher Education Institutions,
Grant/Award Number: 1107047002; Fun-
damental Research Funds for the Central
Universities, Grant/Award Numbers:
3
2
207046409, 3207047402 and
242015 k30001; Transformation of Scien-
tific and Technological Achievements of
Jiangsu Province of China, Grant/Award
Number: BA2014100; Scientific Research
Foundation of Graduate School of South-
east University, Grant/Award Numbers:
YBJJ1731, YBJJ1733 and YBJJ1732; Grad-
uate student scientific research innovation
program of Jiangsu Province, Grant/
Award Number: KYCX17_0136
KEYWORDS
alkylation, catalyst, mesoporous poly ionic liquid, P123
KYCX17_0134; Qing Lan Project of
Jiangsu Province, Grant/Award Number:
1107040167; Jiangsu Province of China,
Grant/Award Number: JNHB‐006;
National Natural Science Foundation of
China, Grant/Award Numbers: 51673040,
21376051 and 21676056
Appl Organometal Chem. 2019;e4719.
wileyonlinelibrary.com/journal/aoc
© 2019 John Wiley & Sons, Ltd.
1 of 12
https://doi.org/10.1002/aoc.4719

2
of 12
WANG ET AL.
[
22–25]
1
| INTRODUCTION
chemistry.
As a burgeoning interdisciplinary topic,
PILs are attracting increasing interest due to the
combination of the unique properties of IL with the mac-
romolecular architecture and creating new properties
The Friedel‐Crafts (F‐C) reaction 1–3] is a key direct C‐C
bond forming reaction, which is one of the cornerstones
of organic and industrial synthetic chemistry. For exam-
[
[
26–28]
and functions.
Recently, a series of PIL materials
[4]
ple, Phenylxylylethane (PXE) obtained by the alkylation
of o‐xylene with styrene has been widely used as excellent
solvent. Generally, a strong acid catalyst such as H SO ,
have been synthesized by introducing functional cationic
and anionic IL groups into dynamic macromolecular poly-
meric architectures which have broadened PIL properties,
2
4
[
29–32]
AlCl and Phosphotungstic acid (HPW) is essential to the
structures, functionalities and applications.
PILs
3
F‐C reaction. However, for traditional alkylation catalysts,
have been widely used in catalysis due to the function‐
[5]
[33–35]
there were series of disadvantages, for instance, strong
corrosivity, unstability, dangerous to handle and over‐
alkylation of the product, etc. Furthermore, the separation
of catalysts from catalytic system is difficult. Facing to
these problems, much efforts are still necessary to design
and synthesize environmental catalysts with stable physi-
cochemical properties and superior catalytic performance.
designability and eco‐friendly quality.
For example,
Ali Pourjavadi and cooperators synthesized a dual acidic
heterogeneous organocatalyst by copolymerization of
acidic ionic liquid monomer ([VSim][HSO ]) and liquid
4
crosslinker (1,4‐butanediyl‐3,3‐bis‐l‐vinyl imidazolium
[
36]
dihydrogen sulfate).
The catalyst was shown to be an
efficient dual acidic organocatalyst for Biginelli reaction
under mild reaction conditions in high yields. Junke Wang
et al. prepared a novel poly(4‐vinylpyridine) supported
acidic ionic liquid catalyst which acted as a heterogeneous
catalyst to effectively catalyze the cyclocondensation reac-
[
6–9]
Recent research reveals that porous materials
are
favorable carrier and catalyst due to their high surface area
and much ordered channels. Porous materials (such as
[
10]
[11,12]
mesoporous silicon,
porous carbon,
macroporous
[13]
polymers,
neous catalysis.
etc.) have a profound impact on heteroge-
tion of anthranilamide with aldehydes under ultrasonic
[
14–16]
[37]
For instance, Sai An et al. prepared
irradiation.
Except for the above studies, some
a series of Arenesulfonic acid functionalized ethyl‐bridged
researchers and scholars started to report porous PILs
materials. That is to say, it's feasible to design and synthe-
size porous PILs which possess high surface areas and
large pore volume. For instance, Zuowang Wu et al. pre-
organosilica hollow nanospheres, ArSO H‐EtHNS, with
3
[17]
different shell thicknesses (2–6 nm).
The ArSO H‐Et‐
3
HNS has an excellent catalysis performance in the
hydrolysis of furfuryl alcohol (FAL) to levulinic acid
pared
a Brønsted acidic PILs with Multi‐layered
(LA). Christopher B. Smith et al. obtained Carbon‐based
macroporous structure which proved to be a novel and
solid acid catalyst from water hyacinth leaves by one‐step
hydrothermal carbonization, the presence of highest
amount acid sites in the materials promote esterification
efficient heterogeneous acidic catalyst for biodiesel pro-
[
38]
duction.
Jing li and cooperators obtained
a
heteropolyanion‐based acidic ionic liquid‐functionalized
[18]
2
of oleic acid and dehydration of xylose.
Previously,
mesoporous copolymer P (VB‐VMS) PW (SBET = 191 m /
our research group conducted extensive research on solid
acid catalysts, including zeolite supported Phosphotung-
stic acid and Zr doped sulfated mesoporous silica.
Nevertheless, some environmental problems and other
drawbacks of these catalysts are still worth deeply ponder-
ing, the most serious problem is the losses of activity sites,
which deriving from destruction of the channels structure.
Poly (ionic liquid) s (PILs) are an emerging class of
functional polymers that are comprised of ionically
charged repeating units typically used in ionic liquid
g), this catalyst shown superior acid catalysis performance
[
39]
in benzylation reaction.
Danuta Kuzmicz et al.
[
19–21]
acquired a series of mesoporous poly (ionic liquid) by
solvothermal copolymerization of divinylbenzene and
monomeric ionic liquids and the PILs which possessed
excellent Physicochemical properties such as thermal sta-
[
40]
bility, acid resistance and high surface areas.
Herein, a novel strategy was proposed for the fabrica-
tion of high‐performance acidic mesoporous poly ionic liq-
uids catalyst. During the fabrication process, with P123
FIGURE 1 Reaction scheme for the synthesis of catalyst PW/MPIL‐S(x)

WANG ET AL.
3 of 12
serve as soft template, mesoporous poly ionic liquids
Divinylbenzene (80.0%w) (D) and 1‐butyl‐3‐vinylim-
(MPILs) was synthesized via one step hydrothermal
idazolium bromide (99.0%w) (C V) were used to synthe-
4
method. Followed by solvent extraction to remove P123.
Later, the anion exchange property of the MPIL materials
allows facile tuning of counter anions, through which the
Keggin‐structured phosphotungstic anion is exchanged
and highly dispersed onto the surface of channels. The
obtained PW/MPIL‐S(x) exhibited perfect catalytic activi-
ties in alkylation of o‐xylene and styrene because of high
surface area and large pore volumes. Besides, the catalyst
not only could be separated and recycled easily, but also
shows high thermal and mechanical stability, thereby
indicating the wide application fields in acidic catalysis.
Figure 1 clearly shows reaction scheme for synthetic pro-
cesses of catalyst.
size poly ionic liquid which supplied by Energy chemical
Co., Ltd. 2, 2′‐Azobis (2‐methylpropionitrile) (AIBN) were
purchased from Aladdin Industrial Corporation. Phospho-
tungstic acid (HPW), acetonitrile (AR) (MeCN), tetrahy-
drofuran (AR) (THF) and ethanol absolute (AR) (EtOH)
were purchased from Sinopharm Chemical Reagent Co.,
Ltd. Styrene and o‐xylene were supplied by Shanghai
Lingfeng Chemical Reagent Co., Ltd.
2.2 | Catalyst synthesis
2.2.1 | Preparation of uniform size meso-
porous poly ionic liquids materials
2
2
| EXPERIMENTAL
.1 | Materials
The uniform sized mesoporous poly ionic liquid (MPIL)
were synthesized in analogy to a method described by
[
41]
Chenjue Gao et al.
The synthesis was achieved
through free radical copolymerization of D with C V in
4
All chemicals were analytical grade and were used
as received without further purification. P123
the presence of amphiphilic soft templates P123. In a typ-
ical reaction, 3.0 g P123 was dissolved using 30 ml THF.
(
PEO PPO PEO ) was purchased from Sigma‐Aldrich.
Subsequently, 2.31 g ionic liquid monomer C V and
20
70
20
4
FIGURE 2 FT‐IR spectra (a‐b) and TG curves (c) of samples, EDS elemental mapping analysis (d‐f) of the catalyst PW/MPIL‐THF(3.0g)

4
of 12
WANG ET AL.
2
.60 g DVB were added into above clear homogenous
stirred at room temperature for 72 hr. Afterward, the
white solid was collected by filtration and washed with
ethanol for three times. After a vacuum drying at 60 °C
for 24 hr, PW/MPIL‐S(x) was obtained.
P123 solution with stirring more than 3 hr, in order to
form well‐dispersed micelles. Then 0.15 g AIBN was added
to the mixture. After vigorous stirring 3 hours at room
temperature, the mixture was transferred into 100 ml Tef-
lon lined stainless steel autoclave for reacting at 100 °C for
2
4 hr. Then the white or yellowish solid was collected by
filtration, washed with ethanol three times and dried
under vacuum at 60 °C. Finally, the template was remove
by extracting in HCl solution (150 ml ethanol and 1 ml
concentrated aqueous HCl, 36–38%).
Similarly, a series of samples were synthesized by
changing solvent or the amount of P123 during
synthesis. The final products were named as MPIL‐S(x),
where S stands for the solvent and x means the
amount of P123. As a comparison, samples without P123
were also prepared.
2.3 | Catalyst characterization
Scanning electron microscopy (SEM) images were
recorded on a JEOL JSM‐5600 L SEM instrument. Trans-
mission Electron Microscopy (TEM) images were mea-
sured using FEI Tecnai G20 instrument. Specific surface
areas and pore size distributions were carried out by
Brunauer–Emmett–Teller (BET) method at −196 °C under
an ASAP 2020 system, and the samples were outgassed in
the degas port of the apparatus at 80 °C for 3 hr prior to
testing. The pore size distribution in mesoporous range
was analyzed by the BJH (Barrett–Joyner–Halenda)
method. Fourier transform infrared (FT‐IR) spectra
were recorded on a BRUKERALPHA FT‐IR spectrometer.
FT‐IR spectrophotometer using anhydrous KBr as stan-
dard (1 wt% of the sample). Thermo Gravimetric Analysis
(TGA) was performed using a Rigaku ThermoPlus TG8120
2
.1.1 | Synthesis of acidic mesoporous poly
ionic liquids (PW/MPIL‐S(x))
Acidic mesoporous poly ionic liquids were prepared by
impregnation according to the approach reported in the
[42]
−1
literature with a slight modification.
In a typical
system at a rate of 10 °C min under air. The X‐ray
procedure, MPIL‐S(x) (0.5 g) was added to 200 ml of the
photoelectron spectroscopy (XPS) spectra were performed
ethanol solution of 3.0 g HPW, and the mixture was
on a Thermo ESCALAB 250 with Al Kα radiation.
FIGURE 3 SEM images of samples: (a) MPIL‐THF(3.0g), (b) MPIL‐EtOH(3.0g), (c) MPIL‐MeCN(3.0g), (d) PW/MPIL‐THF(0.0g), (e) PW/
MPIL‐THF(1.0g), (f) PW/MPIL‐THF(2.0g), (g) PW/MPIL‐THF(4.0g), (h) PW/MPIL‐THF(3.0g)

WANG ET AL.
5 of 12
2
.4 | Catalytic tests
to the reactor at the reaction temperature, followed by
the desired amount of catalyst, the mixture of 4.0 g styrene
and 10.0 g o‐xylene was dripped slowly (about 2 hr) to the
reaction mixture at the same temperature and continue to
react for 1 hr. After the reaction, catalyst was recycled by
vacuum filter and unreacted o‐xylene was distilled out
under atmospheric pressure, then a collected part was
called as crude product. The crude product was analyzed
with GC‐9890A gas chromatograph equipped with OV‐1
The alkylation reactions were carried out in a continu-
ously stirred batch reactor under reflux conditions using
a three‐neck 100 ml round‐bottom flask equipped with a
condenser. Preliminary runs were conducted with 4.0 g
of styrene, 30.0 g of o‐xylene (quality ratio of o‐xylene to
styrene, 7.5:1) and 0.25 g of catalyst at 120 °C for
1
80 min. At first, the 20.0 g o‐xylene was initially added
FIGURE 4 TEM images of samples: (a) MPIL‐THF(3.0g), (b) MPIL‐EtOH(3.0g), (c) MPIL‐MeCN(3.0g), (d) PW/MPIL‐THF(0.0g), (e) PW/
MPIL‐THF(1.0g), (f) PW/MPIL‐THF(3.0g)
FIGURE 5 (a) N2 adsorption–desorption isotherms of (a) MPIL‐THF(0.0g), (b) MPIL‐THF(1.0g), (c) MPIL‐ For Peer Review THF(2.0g), (d)
MPIL‐THF(3.0g), (e) MPIL‐THF(4.0g), (f) MPIL‐EtOH(3.0g) and (g) MPIL‐MeCN(3.0g). (b) Pore size distribution calculated by BJH model
based on desorption curves

6
of 12
WANG ET AL.
capillary column and a flame ionization detector (FID).
The yield of PXE was defined as follows:
The surface morphologies of the samples synthesized
from different solvent or different P123 dosage
were investigated by SEM (Figure 3). Almost all
samples displayed a similar morphology of sphere‐like
aggregation. It can be clearly found the differences among
the MPILs prepared in different solvents from Figure 3(a‐
c), among them, MPIL‐THF (3.0 g) had more fluffy struc-
ture than the others. The dosage of P123 had a significant
influence on morphology of PW/MPIL‐THF(x). The shape
of PW/MPIL‐THF (0.0 g) was a monolith, on the contrary,
the structure of catalyst had turn into sphere‐like aggrega-
tion in the presence of P123, what's more, when the dosage
of P123 increased to 4.0 g, the size of primary sphere‐
shaped particles up to 3–4 μm.
Yield of PXE ð%Þ ¼ actual product weight=
theoretical product weight*100%
(1)
actual product weight ¼ crude product
weight*PXE ðchromatographyÞ%
3
| RESULTS AND DISCUSSION
3.1 | Catalyst characterization
The pore structure of the samples was further studied
by TEM (Figure 4). By observing MPILs which prepared
with different solvent from Figure 4 (a‐c), the obvious
mesoporous structure was discovered easily in MPIL‐
THF (3.0 g). Thus, a series of catalysts were synthesized
which using tetrahydrofuran as a solvent with different
amounts of P123. By comparing TEM images of
PW/MPIL‐THF(x) (Figure 4(d‐f)), it's self‐evident to con-
firmed that with the increase of the dosage of P123, the
channel size became uniform. Meanwhile, the channel
structure of PW/MPIL‐THF (3.0 g) was consistent with
MPIL‐THF (3.0 g), it proved that MPILs kept high stabil-
ity during the preparation process. Also, the exposure of
active sites benefited from abundant mesoporous struc-
ture and eventually strengthened the catalytic activity.
The porosity of MPIL‐S(x) is investigated by N2
adsorption–desorption experiments. As displayed in
Figure 5(a), all the samples exhibited the typical IV
adsorption isotherms, which indicated the presence of
mesoporous structures. Correspondingly, the pore size
distribution (Figure 5(b)) was consistent with TEM. In
addition to MPIL‐THF (0.0 g), all samples shown only
one peak at 4.5 nm which owed to the mesoscale micelles
As shown in the above FT‐IR spectra (Figure 2 a‐b), all
samples exhibited a series of characteristic peaks, included
−
1
−1
−1
−1
3
435 cm , 1650 cm and 1560 cm , 1460 cm etc.,
which attributed to N‐H stretching vibration, C=O
stretching vibration and C=N stretching vibration of
imidazole ring skeleton, imidazole ring C‐H deformation
vibration. Besides that, the observation of strong band at
−
1
2
860–2960 cm were indicative of stretching vibrations
of the C‐H group. By observing FT‐IR of MPIL which pre-
pared in different solvents, no obvious difference was
−
1
found. It can be seen clearly that the 1082 cm (P‐O in
−
1
the central tetrahedron), 980 cm
8
(terminal W=O),
−
1
−1
96 cm and 812 cm (W–O–W) in PW/MPIL‐THF(x)
from Figure 5 (b) which associated with Keggin ion.
[
43]
This proved the Keggin structure of 12‐tungstophosphoric
acid was appeared after anion exchange with HPW.
Energy‐dispersive X‐ray spectroscopy (EDS) elemental
mapping analysis (Figure 2 (d‐f)) to confirm the immobili-
zation of PW species with a high dispersity which is consis-
tent with FT‐IR of PW/MPIL‐THF(x).
Figure 2 (c) revealed the thermal stability of the
samples. By comparing the image of TG curves, it can
be find that all samples shown three thermal decompo-
sition segments. At the first part, the decomposition
maybe refer to solvent and physical adsorbed water
TABLE 1 Physicochemical properties of the MPIL‐S(x) which
prepared at different condition
(
weight loss≤1%). Then the bond of copolymer of C V
4
Sample
Name
BET Surface Pore Volume Average Pore
and D start to rupture at 300 °C. Finally, the whole
structure of MPIL was decomposed thoroughly about
2
3
Area (m /g) (cm /g)
Size (nm)
MPIL‐THF(0.0 g)
MPIL‐THF(1.0 g)
MPIL‐THF(2.0 g)
MPIL‐THF(3.0 g)
MPIL‐THF(4.0 g)
37
452
513
589
737
197
0.22
0.47
0.77
1.03
1.16
0.25
29.01
3.66
5.94
9.01
8.67
6.79
5
50 °C. In last decomposition part, PW/MPIL‐THF(x)
were different from MPIL which appeared in MPIL
almost completely degraded but PW/MPIL‐THF(x)
would not due to Keggin structure of 12‐tungstop-
hosphoric acid. What's more, PW/MPIL‐THF (3.0 g)
has higher stability than PW/MPIL‐THF (0.0 g), and
reused PW/MPIL‐THF (3.0 g) (after 6 times) had a sim-
ilar TG curves of fresh PW/MPIL‐THF (3.0 g). The ther-
mal stability of the catalyst can fully adapt to the
alkylation.
MPIL‐
EtOH(3.0 g)
MPIL‐
MeCN(3.0 g)
97
0.19
10.43

WANG ET AL.
7 of 12
of P123. Detailed physicochemical properties of
short, possessing extremely large surface and pore vol-
ume of samples just like MPIL‐THF (3.0 g) and MPIL‐
THF (4.0 g), which are beneficial to alkylation reaction
of styrene and o‐xylene.
XPS was performed to analyze the composition and
valenve states of the elements in the PW/MPIL‐THF
(3.0 g). The PW/MPIL‐THF (3.0 g) was composed of
C, N, O, P, W from the XPS wide scan spectrum
(Figure 6a). The C1s spectrum shown a signal peak at
about 284.2 eV, which was assigned to C‐C bonds. The
N1 s spectrum can be deconvoluted into two peaks at
400.1 eV and 401.2 eV, corresponding to N‐C and
N=C bonds, respectively. The P2p spectrum displayed
samples listed in Table 1, MPIL‐THF (3.0 g) possessed
2
larger BET surface area (589 m /g) and pore volume
3
(
(
1.03 cm /g) than MPIL‐EtOH (3.0 g) and MPIL‐MeCN
3.0 g). This consequence caused by P123 aggregation
behavior in different solvent. The dosage of P123 is vital
to textural parameters of MPILs, it can be seen that
with increasing P123 from 0.0 g to 4.0 g, the surface
2
area of each sample is 37, 412, 513, 589 and 737 m /g,
respectively, correspondingly, the pore volume of each
3
sample is 0.22, 0.47, 0.77, 1.03 and 1.16 cm /g. To a
great extent, the BET surface area and pore volume of
MPILs enlarged with the increase of P123 content. In
FIGURE 6 XPS wide scan spectra of PW/MPIL‐THF(3.0g) (a) and C1s, N1s, P2p and W4f of PW/MPIL‐THF(3.0g) (b‐e)

8
of 12
WANG ET AL.
a wide signal peak at about 133.8 eV, ascribing the
monomer C V and DVB fully disperse on the micelle
4
5+
existence of P
in the oxidation state. Additionally,
surface, the third part polymerization process can take
place on schedule. Subsequently, removing the template
by solvent extraction and preparing catalyst PW/MPIL‐
S(x) by anion exchange. The difference of physicochem-
ical properties of different samples maybe ascribe to
P123 micelles distinction which caused by P123
aggregation behavior at different solvents and different
dosages. Meanwhile, there is an interaction between
the W4f spectrum is deconvoluted into two significant
peaks at 35.1 eV (4f5/2) and 37.2 eV (4f7/2), respectively,
which are typically attributed to W in the W–O bond
6+
[44]
configuration and W
in HPW.
Combining XPS
spectrum of P2p and W4f, it can be verify Keggin
structure of 12‐tungstophosphoric acid was loaded in
the mesoporous channels successfully. The result was
corresponding with Energy‐dispersive X‐ray spectros-
copy elemental mapping analysis and FT‐IR of PW/
MPIL‐THF (3.0 g).
P123 and IL monomer C V which mainly due to the
4
hydrogen bond. So the interaction between P123 and
C V is different with the increase of P123, when the
4
Figure 7 reveals conjectural formation mechanism of
PW/MPIL‐s(x): as we all known, triblock P123 mole-
cules can self‐assemble into the mesoscale micelles in
aqueous systems due to the hydrophobic core and the
hydrophilic head group of amphiphilic molecules. On
account of this, P123 plays an important role in the
structure‐directing aspect. During the synthesis of inor-
ganic silicon materials, P123 usually is used as template
because of the advantages of superior pore regulation
effect. The polymerization process includes three parts.
At first, forming a uniform transparent P123 micelle
solution. The size of P123 micelles is different in
different solution which affects pore size and pore size
distribution of followed synthetic polymer. Then the dis-
dosage of P123 is low, the interaction between P123
and C V is weak. It's evident that the physicochemical
4
properties of MPIL are affected by various factors. In
general, the BET surface become lager with the increase
of the dosage of P123 according to Table 1, at the same
time, narrow pore size distribution is beneficial to
catalytic reactions. Appropriate pores promote reactant
molecules to contact with active sites and diffusion
of products.
3.2 | Catalytic assessment
The Friedel‐Crafts (FC) reaction is a key direct carbon–
carbon bond forming reaction widely is used to prepare
organic intermediates and employed for evaluating cata-
lytic activity of the obtained mesoporous copolymeric
solid acids. Table 2 listed the styrene conversion and
PXE yield which using different catalyst precursor.
According to the results, it can be clearly seen that
HPW has excellent activities both yield (100%) and
selectivity (100%) for this reaction, it's consistent with
persion process of ionic liquid monomers C V and
4
cross‐linker DVB is a critical intermediate process.
Crosslinking polymerization process on micelle surface
is the third section, in this stage, P123 micelles were
wrapped by cross‐linked polymerization products.
Besides that, P123 micelles separated IL monomers
which avoid IL homopolymerization or polymerization
particles aggregation to bulk blocks. Only ionic liquid
FIGURE 7 Hypothetical formation mechanism of PW/MPIL‐S(x) catalyst

WANG ET AL.
9 of 12
TABLE 2 Yield of PXE and conversion of styrene in the alkyl-
ation of o‐xylene and styrene
pure HPW, this catalyst was simply separated from mix-
ture. As displayed in Table 2, it's obvious to find that all
catalysts exhibit high PXE yield and good selectivity,
indicating that PW/MPILs catalyst was prepared suc-
cessfully via anion exchange with HPW. Among them,
PW/MPIL‐THF (3.0 g) and PW/MPIL‐THF (4.0 g) exhib-
ited the highest styrene conversion (100%). On the
contrary, the catalyst activity of PW/MPIL‐THF (0.0 g)
was unsatisfactory with the styrene conversion and.
PXE yield were 60.25% and 49.26%, respectively. By
observing TEM image (Figure 3(d)) and BET (Figure 4
and Table 1), it can be find that the structure of MPIL‐
THF (0.0 g) was disadvantageous for the reaction, such
as, low surface and pore volume. Therefore, the excellent
catalytic performance of catalyst attributed to both the
favorable structure and strong acid sites.
Additionally, the influence of reaction conditions was
investigated systematically and displayed in Figure 8(a‐b).
Experiments were conducted under catalyst PW/MPIL‐
THF (3.0 g). The dosage of catalyst was verified as signif-
icant factor. According to Figure 8 (a), when the amount
of catalyst from 0.05 g add up to 0.25 g, the conversion of
styrene increase obviously. Whereas, when the dosage of
catalyst from 0.25 g to 0.35 g, the selectivity decrease
gradually. This consequence explained that overmuch
Styrene
PXE
Catalyst
Conversion (%)
Yield (%)
HPW
100
100
PW/MPIL‐EtOH(3.0 g)
PW/MPIL‐MeCN(3.0 g)
PW/MPIL‐THF(4.0 g)
PW/MPIL‐THF(3.0 g)
PW/MPIL‐THF(2.0 g)
PW/MPIL‐THF(1.0 g)
PW/MPIL‐THF(0.0 g)
92.51
83.15
100
87.34
82.26
95.44
96.21
92.26
89.51
49.26
100
97.88
91.59
60.25
[45]
Sheng et al.
Nevertheless, it is difficult to purify pro-
duction after reaction. At moment, the PW/MPIL‐S(x)
shows superiority which including abundant acid sites
thanks to larger surface and pore volume, non‐corrosive,
environmentally friendly. What's more, compared with a
FIGURE 8 Effect of the catalyst (PW/MPIL‐THF(3.0g)) dosage (a), reaction temperature (b) and reaction time (c) on the conversion of
styrene and selectivity of PXE. (Reaction condition: T=393 K, catalyst dosage=0.25 g, t=3.0 h). (d) Cycling performance test of PW/MPIL‐
THF (3.0g)

10 of 12
WANG ET AL.
FIGURE 9 Recycling of catalyst (PW/MPIL‐THF(3.0g)) FT‐IR spectrum of before reaction and after reaction(a), N2 adsorption‐desorption
isotherms and pore size distribution (inset) of fresh catalyst and recovered catalyst (b), SEM image (c), TEM image (d)
catalyst is disadvantageous to reaction. For a defined cat-
alytic system, too much catalyst will cause side reactions.
Therefore, the appropriate amount of catalyst addition is
important to the reaction. In this reaction, the optimal
dosage of catalyst is 0.25 g (6.25% of styrene quality).
Figure 8(b) explored the effect of reaction temperature
on the conversion of styrene and selectivity of PXE. Reac-
tion temperature is another crucial factor to the catalyst
reaction. The level of temperature determines whether
the reaction can occur and the extent of side reactions.
By analyzing the curves of conversion of styrene and
selectivity of PXE in Figure 8 (b), it can be discovered eas-
ily that when the temperature was below 70 °C, the con-
version of styrene was only 36.5%. With increasing of
reaction temperature, the conversion of styrene increased
significantly, the selectivity of PXE increased as the reac-
tion temperature went up, in agreement with the conver-
sion of styrene. What is noteworthy is that when the
temperature exceed 120 °C, the selectivity of PXE start
decreasing. When the reaction temperature exceed
Reaction time also influences the conversion of sty-
rene and selectivity of PXE. Figure 8 (c) expressed intui-
tively this result. When the process of reaction time
from 2.0 hr to 4.0 hr, the conversion of styrene increased
accordingly, later reached constant (100%) after 3 hr. On
the contrary, the PXE selectivity trend curve was different
with the conversion of styrene curve, the best selectivity
obtained when reacted for 3 hr. In summary, the optimal
reaction time is 3 hr.
3.3 | Catalyst recycling
Stability and reusability of the catalyst are crucial for any
catalytic system. The cycling of the catalyst PW/MPIL‐
THF (3.0 g) has been tested via carrying out the reaction
with used catalyst under the optimized conditions. The
cycling results were summarized in Figure 8(d). It can
be seen only 13% reduction in the activity is observed
after 5 runs for the catalyst PW/MPIL‐THF (3.0 g). The
catalyst PW/MPIL‐THF (3.0 g) was prepared by anion
exchange, thus, it's difficult to loss the acid sites because
of the strong interaction of the active composition and
1
20 °C, the side reactions maybe occur, such as polymer-
ization of styrene, polysubstituted of benzene ring, etc.
That is to say, 120 °C is the suitable reaction temperature

WANG ET AL.
11 of 12
support. And the PXE yield reached 84% after 5 times.
Compared pure HPW, there was a little reduction of the
conversion of styrene and PXE yield by using recovered
catalyst, however, the PW/MPIL‐THF(3.0 g) possessed
untouchable advantage which including easily to separate
and recycle than HPW.
In order to illustrate the structure and active site dis-
tribution of the recovered catalyst, a series of character-
izations were carried out and the consequences which
displayed in Figure 9. FT‐IR spectra (Figure 9 (a)) exhib-
ited similar characteristic peaks of fresh catalyst and
recovered catalyst, confirming the presence of Phospho-
Jiangsu Province (KYCX17_0134 and KYCX17_0136),
Scientific Research Foundation of Graduate School of
Southeast University (YBJJ1732, YBJJ1733, YBJJ1731),
Fund Project for Transformation of Scientific and Tech-
nological Achievements of Jiangsu Province of China
(Grant No. BA2014100), Fundamental Research Funds
for the Central Universities (2242015 k30001,
3207047402, 3207046409) and A Project Funded by the
Priority Academic Program Development of Jiangsu
Higher Education Institutions (PAPD) (1107047002).
tungstic acid active component. From N adsorption–
ORCID
2
desorption isotherms and pore size distribution (inset)
of fresh catalyst and recovered catalyst, it can be observed
that fresh catalyst possessed larger BET surface area
Beibei Wang https://orcid.org/0000-0001-6550-1074
Chao Zhang https://orcid.org/0000-0002-0143-9504
2
2
(482 m /g) than recovered catalyst (264 m /g) which
because of partial channels were destructed in the reac-
tion. Pore size distribution insert Figure 9 (b) demon-
strated the consistent pore size of fresh catalyst and
recovered catalyst. Which shown mesoporous structure
was preserved well after reaction and verified the high
thermal and mechanical stability of PW/MPIL‐THF
REFERENCES
[1] T. P. Maloney, K. L. Murphy, T. L. Mainsah, K. A. Nolin,
Tetrahedron Lett. 2018, 59, 18.
[2] Y.‐Y. Ding, D.‐F. Xu, S.‐S. Meng, Y. Li, J.‐L. Zhao, Adv. Synth.
Catal. 2018, 360, 664.
[3] S. Singhal, S. Agarwal, S. Arora, N. Singhal, A. Kumar, Catal.
Sci. Technol. 2017, 7, 5810.
(3.0 g). In addition, the SEM image and TEM image of
recovered catalyst (Figure 9(c‐d)) were similar to the fresh
one, verifying a rather durable catalyst structure.
[4] H. Gao, Y. Zhou, X. Sheng, S. Zhao, C. Zhang, J. Fang, B.
Wang, Appl. Catal. A‐Gen. 2018, 552, 138.
[5] X. Fu, X. Sheng, Y. Zhou, Z. Fu, S. Zhao, X. Bu, C. Zhang, RSC
Adv. 2016, 6, 50630.
4
| CONCLUSION
[6] B. Coasne, A. Galarneau, R. J. Pellenq, F. Di Renzo, Chem. Soc.
Rev. 2013, 42, 4141.
In conclusion, a templating approach applied to success-
fully synthesize hierarchical mesoporous poly ionic liquid
materials by using the soft template P123. The channel
structure and physicochemical properties of MPIL‐S(x)
can be adjusted easily by choosing the suitable solvent
and changing the dosage of P123. The MPILs materials
can be easily modified chemically which ascribing to
the special properties of the IL‐like unit in the mesopo-
rous polymer skeleton. So, synthesized heteropolyanion‐
loaded catalyst through exchanging with the acidic
anions. The PW/MPIL‐S(x) exhibited excellent catalytic
activity in alkylation of styrene with o‐xylene. Moreover,
it could be easily recycled for industrially feasible com-
pared to homogeneous catalysts.
[7] S. Chen, P. Li, S. Xu, X. Pan, Q. Fu, X. Bao, J. Mater. Chem. A
2018, 6, 1832.
[8] X.‐H. Li, Y.‐W. Liu, S.‐M. Liu, S. Wang, L. Xu, Z. Zhang, F.
Luo, Y. Lu, S.‐X. Liu, J. Mater. Chem. A 2018, 6, 4678.
[9] E. Yang, E. J. Jang, J. G. Lee, S. Yoon, J. Lee, N. Musselwhite,
G. A. Somorjai, J. H. Kwak, K. An, Catal. Sci. Technol. 2018.
[
10] M. Hartmann, A. G. Machoke, W. Schwieger, Chem. Soc. Rev.
2016, 45, 3313.
[
[
11] Y. Xia, Z. Yang, Y. Zhu, J. Mater. Chem. A 2013, 1, 9365.
12] S. Liu, Y. Liang, W. Zhou, W. Hu, H. Dong, M. Zheng, H. Hu,
B. Lei, Y. Xiao, Y. Liu, J. Mater. Chem. A 2018, 6, 12046.
[
[
[
[
[
13] J. Yin, G. Yang, H. Wang, Y. Chen, Chem. Commun. 2007,
4614.
14] S. S. Chen, T. Maneerung, D. C. W. Tsang, Y. S. Ok, C.‐H.
Wang, Chem. Eng. J. 2017, 328, 246.
15] Y. Wang, D. Zhao, L. Wang, X. Wang, L. Li, Z. Xing, N. Ji, S.
Liu, H. Ding, Fuel 2018, 216, 364.
ACKNOWLEDGEMENTS
16] M. Ran, J. Li, W. Cui, Y. Li, P. Li, F. Dong, Catal. Sci.
Technol. 2018.
The authors are grateful to the financial supports of the
National Natural Science Foundation of China (Grant
No. 21676056, 21376051 and 51673040), “Six Talents Pin-
nacle Program” of Jiangsu Province of China (JNHB‐006),
Qing Lan Project of Jiangsu Province (1107040167), Grad-
uate student scientific research innovation program of
17] S. An, D. Song, Y. Sun, Q. Zhang, P. Zhang, Y. Guo, ACS
Sustainable Chem. Eng. 2018, 6, 3113.
[18] J. Lao, C. B. Smith, S. M. Smith, Chem. – Asian J. 2017, 12, 3178.
[19] S. Zhao, X. Sheng, Y. Zhou, M. He, X. Fu, Y. Zhang, J. Porous
Mater. 2015, 22, 1407.

12 of 12
WANG ET AL.
[
[
[
20] S. Zhao, M. He, Y. Zhou, X. Sheng, X. Fu, Y. Zhang, RSC Adv.
015, 5, 28124.
[37] J. Wang, Y. Zong, R. Fu, Y. Niu, G. Yue, Z. Quan, X. Wang, Y.
2
Pan, Ultrason. Sonochem. 2014, 21, 29.
21] M. Zhang, X. Sheng, Y. Zhang, Y. Zhou, S. Zhao, X. Fu, H.
[38] Z. Wu, C. Chen, Q. Guo, B. Li, Y. Que, L. Wang, H. Wan, G.
Zhang, J. Porous Mater. 2016, 24, 109.
Guan, Fuel 2016, 184, 128.
22] W. Zhang, C. Willa, J.‐K. Sun, R. Guterman, A. Taubert, J.
Yuan, Polymer 2017, 124, 246.
[39] J. Li, Y. Zhou, D. Mao, G. Chen, X. Wang, X. Yang, M. Wang,
L. Peng, J. Wang, Chem. Eng. J. 2014, 254, 54.
[
[
23] M. R. Gao, J. Yuan, M. Antonietti, Chemistry 2017, 23, 5391.
[40] D. Kuzmicz, P. Coupillaud, Y. Men, J. Vignolle, G.
Vendraminetto, M. Ambrogi, D. Taton, J. Yuan, Polymer
24] H. He, D. Luebke, H. Nulwala, K. Matyjaszewski, Macromole-
cules 2014, 47, 6601.
2014, 55, 3423.
[
[
[
[
[
41] C. Gao, G. Chen, X. Wang, J. Li, Y. Zhou, J. Wang, Chem.
Commun. 2015, 51, 4969.
[
[
[
25] A. J. Erwin, W. Xu, H. He, K. Matyjaszewski, V. V. Tsukruk,
Langmuir 2017, 33, 3187.
42] Y. Shi, Z. Guo, Q. Wang, L. Zhang, J. Li, Y. Zhou, J. Wang,
26] Z. Xue, L. Qin, J. Jiang, T. Mu, G. Gao, Phys. Chem. Chem. Phys.
ChemCatChem 2017, 9, 4426.
2
018, 20, 8382.
27] J. Yuan, D. Mecerreyes, M. Antonietti, Prog. Polym. Sci. 2013,
8, 1009.
43] Y.‐L. Peng, J. Liu, H.‐F. Zhang, D. Luo, D. Li, Inorg. Chem.
Fron. 2018.
3
44] H. Wang, C. Wang, Y. Yang, M. Zhao, Y. Wang, Catal. Sci.
Technol. 2017, 7, 405.
[
[
[
[
28] J. Yuan, M. Antonietti, Polymer 2011, 52, 1469.
29] W. Qian, J. Texter, F. Yan, Chem. Soc. Rev. 2017, 46, 1124.
30] S. Hayano, K. Ota, H. T. Ban, Polym. Chem. 2018, 9, 948.
31] T. Zhou, X. Gao, B. Dong, N. Sun, L. Zheng, J. Mater. Chem. A
45] X. Sheng, J. Kong, Y. Zhou, Y. Zhang, Z. Zhang, S. Zhou,
Micropor. Mesopor. Mater. 2014, 187, 7.
2
016, 4, 1112.
[
[
[
[
[
32] A. Dani, K. Tauber, W. Zhang, H. Schlaad, J. Yuan, Macromol.
Rapid Commun. 2017, 38. 1700167
How to cite this article: Wang B, Sheng X, Zhou
Y, et al. Functional mesoporous poly (ionic liquid)
derived from P123: From synthesis to catalysis and
alkylation of styrene and o‐xylene. Appl
33] Y. Zhang, Y. Zhang, B. Chen, L. Qin, G. Gao, ChemistrySelect
2
017, 2, 9443.
34] Z. Guo, Q. Jiang, Y. Shi, J. Li, X. Yang, W. Hou, Y. Zhou, J.
Wang, ACS Catal. 2017, 7, 6770.
Organometal Chem. 2019;e4719. https://doi.org/
35] H. Wang, X. Meng, G. Zhao, S. Zhang, Green Chem. 2017, 19,
10.1002/aoc.4719
1
462.
36] A. Pourjavadi, S. H. Hosseini, R. Soleyman, J. Mol. Catal. A‐
Chem. 2012, 365, 55.