Rosin-based porous heterogeneous catalyst functionalized with hydroxyl groups and triazole groups for CO2 chemical conversion under atmospheric pressure condition

Article abstract of DOI:10.1016/j.reactfunctpolym.2021.104976

Development of efficient, green and recyclable heterogeneous catalysts for the chemical conversion of CO₂ into cyclic carbonates with excellent yields under atmospheric pressure condition is still a very challenging task. Herein, a class of biomass-derived hyper-cross-linked porous heterogeneous catalysts MPAc-Br and MPAc-OH-Br, based on easily available and sustainable rosin, was synthesized by Friedel–Crafts polymerization and the further N-alkylation of triazole groups. Compared with MPAc-Br, the bifunctional catalyst MPAc-OH-Br (bearing triazole IL groups and -OH groups) exhibited higher catalytic activity for direct chemical conversion of CO₂ into cyclic carbonates (up to 99% yields) under metal-, solvent-free and atmospheric pressure conditions. The rosin-based porous molecular structure and bifunctional groups on the surface of MPAc-OH-Br played a very important role in the promoting the cycloaddition of CO₂ with epoxides under the optimal conditions. Furthermore, MPAc-OH-Br exhibited good stability and reusability (96% yield after 10 recycles).

Full text of DOI:10.1016/j.reactfunctpolym.2021.104976

Reactive and Functional Polymers 165 (2021) 104976
Contents lists available at ScienceDirect
Reactive and Functional Polymers
journal homepage: www.elsevier.com/locate/react
Perspective Article
Rosin-based porous heterogeneous catalyst functionalized with hydroxyl
groups and triazole groups for CO2 chemical conversion under atmospheric
pressure condition
Shilin Lai, Jinbin Gao, Xingquan Xiong*
College of Materials Science and Engineering, University of Huaqiao, Xiamen 361021, China
A R T I C L E I N F O
A B S T R A C T
Keywords:
Development of efficient, green and recyclable heterogeneous catalysts for the chemical conversion of CO2 into
cyclic carbonates with excellent yields under atmospheric pressure condition is still a very challenging task.
Herein, a class of biomass-derived hyper-cross-linked porous heterogeneous catalysts MPAc-Br and MPAc-OH-Br,
based on easily available and sustainable rosin, was synthesized by Friedel–Crafts polymerization and the further
N-alkylation of triazole groups. Compared with MPAc-Br, the bifunctional catalyst MPAc-OH-Br (bearing triazole
IL groups and -OH groups) exhibited higher catalytic activity for direct chemical conversion of CO2 into cyclic
carbonates (up to 99% yields) under metal-, solvent-free and atmospheric pressure conditions. The rosin-based
porous molecular structure and bifunctional groups on the surface of MPAc-OH-Br played a very important role
in the promoting the cycloaddition of CO2 with epoxides under the optimal conditions. Furthermore, MPAc-OH-
Br exhibited good stability and reusability (96% yield after 10 recycles).
Rosin-based porous polymers
CO2
Cyclic carbonates
Atmospheric pressure
1. Introduction
the development of highly efficient catalysts for the production of value-
added cyclic carbonates from CO2 is currently a hot point from the
Since the industrial revolution, the mass consumption of fossil fuels
and a large number of carbon dioxide (CO2) emissions have led to the
increasing concentration of CO2 in the air year by year, seriously
destroying the natural carbon cycle, resulting in a series of serious
environmental and social problems [1,2]. Thus, the chemical fixation
and conversion of CO2 into commercially relevant fine chemicals has
attracted much public attention since CO2 is a cheap, easily available,
and environmentally friendly renewable C1 resource [3–7]. The chem-
ical conversion of CO2 can not only reduce CO2 emissions, but also
provide a green technological route, which is of great significance for
green and sustainable social development [8–10]. Among them, the
chemical conversion of CO2 with terminal epoxides into cyclic carbon-
ates through a cycloaddition reaction is the most promising strategy due
to 100% atom economy [11–16]. The cyclic carbonate products are
green solvents in the field of catalysis, and used extensively as precursors
in organic synthesis as important intermediates in the synthesis of fine
chemicals.
viewpoint of green synthesis chemistry. Up to now, a series of catalysts
have been developed for the production of cyclic carbonates through
CO2 cycloaddition, such as ionic liquids (ILs) [20–22], metal complex
catalysts [23–25], porous materials [26–31], bifunctional dendrimer
[32], organocatalysts [33–35]. Although most of the catalytic systems
show good to excellent yields of cyclic carbonates, high CO2 pressure are
always needed in these studies. To further enhance the efficiency of
chemical fixation of CO2 with epoxides into cyclic carbonates relatively
mild reaction conditions, great efforts have been focused on the prepa-
ration of highly efficient and sustainable catalytic systems [36,37].
Task-specific ionic liquids (ILs), regarded as efficient and green ho-
mogeneous catalysts, have been extensively used in the field of chemical
fixation of CO2 into cyclic carbonates. The functional ILs, especially the
–
–
–
NH2, OH, or COOH functionalized ones, could exhibit obviously
enhanced catalytic activities for the chemical fixation of CO2 with ep-
oxides. Unfortunately, these homogenous ILs catalysts are often expen-
sive, difficult biodegradable, sometimes toxic, which limit their
industrial applications. Furthermore, the homogenous ILs catalysts are
minimally recyclable and, therefore, are not desirable for industrial
However, the kinetic inertness and thermodynamic stability of CO2
make it a great challenge to activate this greenhouse gas [17–19]. Thus,
* Corresponding author.
E-mail address: xxqluli@hqu.edu.cn (X. Xiong).
https://doi.org/10.1016/j.reactfunctpolym.2021.104976
Received 5 May 2021; Received in revised form 4 July 2021; Accepted 7 July 2021
Available online 10 July 2021
1381-5148/© 2021 Elsevier B.V. All rights reserved.

S. Lai et al.
Reactive and Functional Polymers 165 (2021) 104976
O
O
O
O
O
O
Br
Tri-alkyne MPAc
O
C
n
li
o
i
c
t
k
r
ac
e
e
a
r
c
NaN3, CuBr, DMF, MW
NaN3, CuBr, DMF, MW
k
t
i
o
c
i
l
n
C
O
O
O
O
N
O
N
N
N
N
N
N
N
HO
HO
N
N
O
O
O
N
N
N
N
N
O
N
N
N
O
OH
O
O
MPAc-triazole-OH
MPAc-triazole
FDA, DCE, FeCl3
FDA, DCE, FeCl3
HCPs-OH
HCPs
Br
Br
DMF, 80oC, 24h
DMF, 80oC, 24h
Br
N
N
O
O
N
N
O
Br
N
N
HO
HO
O
N
O
N
N
N
N
Br
O
Br
O
N
N
O
N
N
N
O
OH
N
N
Br
Br
O
O
O
MPAc-OH-Br
MPAc-Br
Fig. 1. Schematic illustration of the fabrication of rosin-based hyper-cross-linked porous heterogeneous catalysts MPAc-OH-Br and MPAc-Br via the Friedel–Crafts
reaction, followed by post-modification with n-butyl bromide using the triazole groups on the surface.
purposes. To solve the above problems, an alternative to homogenous
ILs catalysts in cyclic carbonates synthesis requires further research.
Nowadays, porous ionic networks (PINs) have been widely used in the
field of functional materials [38–41]. PINs present some of the unique
properties of ILs (thermal/chemical stability, and ionic conductivity)
together with excellent catalytic performance. So far, several PINs cat-
alysts have been reported as efficient catalysts for cyclic carbonate
production [42–47]. However, all the PINs catalysts are made from non-
renewable sources, which will result in environmental problem and cost
issue. Therefore, it is still highly desirable to develop low-cost, highly
efficient, environmentally friendly but easily prepared heterogeneous
catalysts for chemical fixation of CO2 with epoxides.
resources, as one of the most abundant natural resources, rosin has been
extensively used as raw material in the organic chemistry because of
their renewable and low-cost properties. Compared with the obvious
achievements made with traditional polymeric materials derived from
fossil oil, the development of polymers prepared from renewable natural
resources has been limited. As a kind of important renewable natural
resource, rosin and its derivatives have been used widely in the field of
modern chemical production industry as chemical raw materials, which
not only enhances the value of natural resource but also reduces the
dependence on fossil oil resources [49,50]. The potential for chemical
modification of rosin and its derivatives also makes them valuable bio-
based monomers in the synthesis of polymeric materials. Therefore,
rosin-based monomers are potential substitutes for the petroleum-based
monomers used in polymers.
With the declining petroleum resources and associated the environ-
mental problems caused by the rapid industrial development, the design
and synthesis of sustainable bio-based materials has received wide-
spread attention both in academia and industry [48]. In recent years,
due to the rising environmental awareness and depletion of fossil
In continuation of our efforts to develop efficient and cost-effective
approaches for the synthesis of cyclic carbonates [51,52], we report
here
a
new kind of bifunctional hyper-cross-linked porous
2

S. Lai et al.
Reactive and Functional Polymers 165 (2021) 104976
O
COOH
O
O
O
O
120 oC, N2, 1 h
COOH
1) KOH/EtOH
O
CH3COOH, 120 oC, 3 h
2) HCl (6%)
COOH
COOH
COOH
COOH
MPAc (Yield 85%)
MPA (Yield 64%)
LPA
Rosin
O
N
N
O
N
N
HO
HO
O
N
N
O
O
N
N
N
O
NaN3, CuSO4, NaAs
OH
O
O
O
O
O
Br
MPAc-triazole-OH (Yield 90%)
DMF, 85 oC, 24 h
O
Br
N
N
O
O
O
N
N
NaN3, CuSO4, NaAs
Tri-alkyne MPAc (Yield 56%)
N
N
O
O
N
N
O
N
O
MPAc-triazole (Yield 90%)
Scheme 1. Synthesis of bio-based monomer MPAc-triazole-OH and MPAc-triazole from rosin.
heterogeneous catalyst MPAc-OH-Br (bearing triazole IL groups and
2.2. Instruments
–
OH groups) from rosin for green and low-cost preparation of cyclic
carbonates from CO2 and epoxides under metal-, solvent-free and at-
mospheric pressure conditions (Fig. 1). In addition, the porous polymer
MPAC-Br without hydroxyl functionalization was used as a contrast.
Obviously, the rosin-based porous molecular structure and bifunctional
groups on the surface of MPAc-OH-Br played a key role in the promoting
the cycloaddition of CO2 with epoxides under the optimal conditions.
The inherent rigid structure of rosin-based porous heterogeneous cata-
lyst can not only promote gas adsorption process in an entropic manner,
but only enhance the thermal and chemical stabilization of material.
Furthermore, the porous structure increases the specific surface area of
MPAc-OH-Br, and the hydroxyl groups are able to coordinate to the
epoxide through hydrogen bonding and enhance the activity for this
reaction.
FT-IR spectra were recorded on a Nicolet Nexus FT-IR instrument at
4 cmꢀ 1 resolution and 32 scans and samples for FT-IR analysis were
prepared using the KBr press disc method. 1H NMR spectra were
recorded on a Bruker AVANCE III-500 spectrometer. TGA was carried
◦
out run in Ar atmosphere with a heating rate of 20 C/min on TG in-
struments DTG-60H. The scanning electron microscopy (SEM) obser-
vation was performed on a HitachiSU8020 microscope operated at a 3
kV/10 μA accelerating voltage. The organic element analyzer was per-
formed on a 230 V/EURO E device manufactured by Leeman China. The
polymer surface areas, N2 adsorption isotherms (77.3 K) and pore-size
distributions were measured using a Micromeritics 3Flex surface area
and porosity analyzer. Before analysis, the samples were degassed at
150 ◦C for 8 h under vacuum (10ꢀ 5 bar). The yields of the obtained
products are isolated yields.
2. Experimental section
2.3. Preparation of malaypimaric anhydride
2.1. Chemicals and reagents
The preparation of malaypimaric anhydride (MPA) were carried out
according to the similar procedure described in other literatures
[53,54]. In a three-necked round-bottomed flask (250 mL) equipped
with a magnetic stirrer and a reflux condenser, rosin acid (75% purity,
20 g) and CH3COOH (50 mL) was heated to 120 ◦C. Then, the mixture is
refluxed for two hours under N2 atmosphere to complete the isomeri-
zation of abietic acid. To this mixture were added 8.0 g of maleic an-
hydride (81.6 mmol) and the reaction mixture was refluxed for three
hours. Then, 20 mL of CH3COOH were added into the reaction mixture.
After the reaction mixture was cooled to room temperature for 24 h, a
white solid MPA was obtained (12.9 g, yield: 64%).
Rosin acid (75%) with an acid number of 166 mg KOH gꢀ 1 was
purchased from Guangxi Wuzhou Pine Chemicals Ltd., China. It was a
mixture of abietic acid and other rosin acids. Maleic anhydride (powder,
99%), propargyl bromide (98%, stabilized with MgO), bisphenol A
diglycidyl ether (≥85%), and 4,4′-bis(chloromethyl)biphenyl (96%)
were obtained from Aladdin Chemicals Ltd. DMF and CH3COOH were
obtained from Xiamen Lvyin Reagent Company. CO2 (99.99%) was
purchased from Xiamen Kongfente Gas Co., Ltd. All chemicals were
obtained commercially and used as received, without further
purification.
3

S. Lai et al.
Reactive and Functional Polymers 165 (2021) 104976
O
O
N
O
O
N
N
N
1) FDA, DCE, FeCl3
O
N
N
N
Br
N
O
2)
N
Br
O
O
N
N
N
O
N
N
O
Br
O
N
N
N
N
Br
MPAc-triazole
O
MPAc-Br
Br
O
O
N
N
O
O
N
N
N
N
N
N
HO
HO
HO
HO
N
N
O
1) FDA, DCE, FeCl3
O
N
N
O
N
2)
O
N
N
O
Br
OH
N
N
N
O
OH
Br
O
Br
O
MPAc-triazole-OH
MPAc-OH-Br
Scheme 2. Synthesis of the rosin-based hyper-cross-linked porous heterogeneous catalysts MPAc-Br and MPAc-OH-Br.
2.4. Preparation of malaypimaric acid
2.6. Synthesis of 1,2,3-triazole-modified monomer MPAc-triazole-OH
from rosin
MPA (50.0 g) was dissolved in hot ethanol (150 mL) in a round
bottom flask (500 mL). The mixture was stirred and the pH value
reached 8–9 by adding an appropriate potassium hydroxide-ethanol
solution. The resulting mixture was stirred continuously until the solid
appeared completely. After that, the rosin-based potassium salt was
collected via filtration and dried in a vacuum oven. Next, the rosin-based
potassium salt (10.0 g) was dissolved in 75% ethanol solution and the
mixture was acidified by 6% dilute hydrochloric acid (mass fraction) at
room temperature. Then, the crude product was completely precipitated
by slowly adding deionized water and obtained via filtration. The crude
product was purified using recrystallization with 75% ethanol to gain
white solid of pure malaypimaric acid (MPAc, 85%).
1,2,3-Triazole-modified rosin-based monomer MPAc-triazole-OH
was prepared by cycloaddition reaction of alkynyl groups of tri-alkyne
MPAc and organic azide using copper sulfate/sodium ascorbate as
catalyst in THF. To a homogeneous solution of tri-alkyne MPAc (0.50 g)
and 2-azido-1-phenylethanol (0.55 g, 3.36 mmol) in 15 mL of THF,
CuSO4/water mixture (0.28 mmol/1.0 mL) and NaOAc/water (0.56
mmol/1.0 mL) were added, and the resulting mixture was vigorously
stirred at room temperature overnight. After removal of the solvent, the
residue was dissolved in ethyl acetate (25 mL) and transferred to a
separatory funnel. Then, the organic layer was washed with brine, dried,
filtered and concentrated. The crude product was purified by column
chromatography on silica gel to obtain MPAc-triazole-OH. The yield of
MPAc-triazole-OH was 90%. The monomer MPAc-triazole was also
synthesized by the similar procedure (Scheme 1).
2.5. Preparation of tri-alkyne MPAc
10.0 g of MPAc (23.9 mmol), 11.8 g of K2CO3 and 30 mL of DMF were
added into a 250 mL one-necked flask to get a white mixture under
magnetic stirring. Then a solution of propargyl bromide (10.2 g, 85.0
mmol) dissolved in DMF (5.0 mL) was added drop by drop. After the
reaction mixture was refluxed at 80 ◦C for 24 h, the reaction was stopped
and cooled slowly to room temperature. And then, the reaction solvent
was removed under reduced pressure on a rotary evaporator. The
product was extracted with EtOAc (3 × 50 mL) and the organic phase
was washed with distilled water (3 × 10 mL). The organic layer was
washed with saturated NaCl solution, dried over anhydrous MgSO4, and
concentrated under reduced pressure to give the crude tri-alkyne MPAc
product. Further purification was performed by silica gel flash column
chromatography with a mixture of PE/EtOAc (4/1) as eluent to afford
the pure tri-alkyne MPAc (yield: 7.13 g, 56%).
2.7. Synthesis of rosin-based porous heterogeneous catalyst MPAc-OH-Br
In an oven dried 50 mL round-bottom flask, MPAc-triazole-OH (2.05
g, 2 mmol), formaldehyde dimethyl acetal (FDA, 1.52 g, 20 mmol) were
dissolved in 15 mL of 1,2-dichloroethane (DCE). Then, anhydrous ferric
chloride (3.24 g, 20 mmol) was added to the above mixture and was
stirred at 45 ◦C for 5 h. After that, the resulting mixture was heated to
◦
85 C and maintained for 48 h to complete the formation of the HCP
network. Upon cooling, the resulting precipitate was collected by vac-
uum filtration and washed twice with ethanol, then further Soxhlet-
extracted by ethanol for 24 h in a Soxhlet extraction unit. Finally, the
obtained polymer HCPs-OH was dried at 80 ◦C under vacuum for 12 h.
HCPs-OH (1.0 g) and 1-bromobutane (1.37 g) was dissolved in DMF
(10 mL) in a round bottom flask (50 mL) and heated at 85 ◦C for 24 h.
Upon cooling, the catalyst was separated by filtration, and the solid was
washed three times with ethanol, and dried under vacuum at 50 ◦C for
4

S. Lai et al.
Reactive and Functional Polymers 165 (2021) 104976
c
a
2870
2961
3424
803
1665
1720
1088
1778
2942
3440
d
e
1712
1726
b
c
2873
2946
1438
2869
2936
1233
1104
835
3296
2129
1724
1654
3413
3437
670
2932
753
802
1029
2870
2961
1456
1726
3066
3424
1665
1183
1105
1778
803
1631
1720
1088
1259
1500
4000
3500
3000
2500
2000
1000
500
4000
3500
3000
2500
2000
1500
1000
500
Wavenumber (cm-1)
Wavenumber (cm-1)
Fig. 2. FT-IR spectra of MPAc (a), tri-alkyne MPAc (b), MPAc-triazole-OH (c), HCPs-OH (d), and MPAc-OH-Br (e).
12 h. The product was named as MPAc-OH-Br. MPAc-Br was also syn-
thesized by the similar procedure (Scheme 2).
f
O
C
f
h
g
e
a
d
b
O
m
2.8. General procedure for chemical fixation of CO2 with epoxides
h
h
c
g
O
i
The chemical fixation of CO2 with epoxides were carried out in a
Teflon-lined stainless-steel reactor (20.0 mL) equipped with a magnetic
stirrer. In the general procedure, epoxide (10.0 mmol), MPAc-OH-Br
(30.0 mg), and TBABr (0.1 mmol, 2.0 mol%) were placed into the
reactor. The reactor was then purged with CO2 three times. Subse-
quently, the reactor was heated to the desired reaction temperature
under the desired pressure condition. After completion of the reaction,
the reactor was removed from the oil bath and then immediately placed
in the iced water bath to quench the reaction. The excess CO2 was
released slowly. EtOAc (15 mL) was added into the reaction mixture,
and then MPAc-OH-Br was recovered by precipitation. Subsequently,
the obtained catalyst was washed two times with EtOAc and dried under
vacuum at 50 ◦C for 5 h for further use.
C
O
l
j
k
f, g, h, i, j, k, l, m
g
C
O
O
g
g
h
h
a
d
b,c
3
e
7
6
5
4
2
1
3. Results and discussion
ppm
Fig. 3. 1H NMR spectrum of tri-alkyne MPAc in CDCl3 with assignment.
3.1. Synthesis of bio-based monomers from rosin
The synthesis route of MPAc-alkyne is shown in Scheme 1. Firstly,
the synthesis of MPAc were carried out according to the similar method
used in previous literatures [53,54]. In the next step, MPAc, K2CO3, and
propargyl bromide were used as raw materials to synthesize tri-alkyne
MPAc. The obtained results showed that esterification of the carboxyl
groups using K2CO3/DMF reaction system resulted in a moderate yield
(24 h, 80 ◦C, 56%). 1,2,3-Triazole-modified rosin-based monomers
MPAc-triazole-OH and MPAc-triazole were prepared by cycloaddition
reaction of alkynyl groups of tri-alkyne MPAc and styrene oxide/NaN3
(or benzyl bromide/NaN3) using copper sulfate/sodium ascorbate as
catalyst in THF.
filtered and washed three times with methanol. The obtained solid was
further purified by Soxhlet extraction methanol for 48 h, and then dried
in a vacuum oven at 50 ◦C for 12 h to obtain HCPs-OH or HCPs. HCPs-
OH or HCPs HCPs-OH (1.0 g) and 1-bromobutane (2.0 mL) was dis-
solved in DMF (10 mL) in a three-necked flask and heated at 80 ◦C for 36
h. After simple filtration and washing with EtOAc, MPAc-OH-Br or
MPAc-Br was obtained and then dried at 50 ◦C for further use.
3.3. Characterization of rosin-based monomer and porous heterogeneous
catalyst
3.2. Synthesis of rosin-based porous heterogeneous catalyst
The chemical structures of the intermediates and tri-alkyne MPAc
were identified by FT-IR, 1H NMR and 13C NMR, respectively. As shown
in Fig. 2a, the peak at 1712 cmꢀ 1 was the stretching coupling vibration
The synthesis route of MPAc-OH-Br is shown in Scheme 2. In this
study, rosin-based MPAc-OH-Br was synthesized by Friedel–Crafts
coupling polymerization and quaternization reaction from rosin-based
monomer MPAc-triazole-OH. Firstly, the obtained bio-based monomer
MPAc-triazole-OH or MPAc-triazole was hyper-crosslinked via Frie-
del–Crafts alkylation coupling reaction with formaldehyde diethyl
acetal (FDA) upon the activation of anhydrous FeCl3 in dichloroethane.
After polymerization at 85 ◦C for 48 h, the brown porous polymer was
–
of the C O bond of carboxylic groups in MPAc. Fig. 2b is the FT-IR
–
spectrum of tri-alkyne MPAc. It can be seen that the broad absorption
peak of carboxylic groups from 3000 to 3500 cmꢀ 1 for MPAc almost
disappeared after esterification of MPAc with propargyl bromide. At the
same time, several new peaks appeared at 3296 cmꢀ 1, 2129 cmꢀ 1, 1726
cmꢀ 1 and 670 cmꢀ 1, which are due to the adsorption of the unsaturated
–
–
– –
–
terminal C C bonds, ester functional groups, and the
C H groups of
–
–
5

S. Lai et al.
Reactive and Functional Polymers 165 (2021) 104976
Fig. 4. 13C NMR spectrum of tri-alkyne MPAc in CDCl3 with assignment.
o
i
O
d
h
p
N
N
q
e
O
O
q
N
g
g
HO
HO
n
b
f
h
n
h
a
O
b
g
g
c
j
N
N
o
q
N
N
i
O
d
q
N
l
k
m
N
p
m
HO
HO
f
O
o
h
q
N
e
N
O
h
OH
f
a
c
i
j
N
N
p
N
N
O
h
q
O
o
i
o
l
k
f, g, h, i, j, k, l, m
O
h
n
N
N
O
OH
N
O
g
o
n
h
C-Ar, a, o, p
b, c, d, e, h
q
H-Ar
n
b
a, o
i, q
g, h
8
7
6
5
4
3
2
1
0
ppm
180
160
140
120
100
80
60
40
20
Fig. 5. 1H NMR spectrum of MPAc-triazole-OH in CDCl3 with assignment.
ppm
Fig. 6. 13C NMR spectrum of MPAc-triazole-OH in CDCl3 with assignment.
tri-alkyne MPAc.
After the click reaction of tri-alkyne MPAc and 2-azido-1-phenyle-
thanol, the peak at 2129 cmꢀ 1 for alkyne groups in the spectrum of
MPAc-triazole-OH have disappeared, and these new emergence peaks
–
– –
C CH. The peaks between 4.45 and
–
corresponded to the protons of
4.70 ppm were assigned to the protons of OCH2C CH. The chemical
–
–
–
–
structure of
COOCH2C CH was further verified using 13C NMR
–
–
–
centered at 3066 cmꢀ 1 and 1665 cmꢀ 1 are related to the stretching vi-
–
–
–
(Fig. 4). After esterification of MPAc with propargyl bromide, the peaks
bration of aromatic C C bonds of benzene rings and triazole rings
–
–
of the carbons in the propargyl groups (a, b, c, d, e and f) in C C bonds
(Fig. 2c). As shown in Fig. 2d and e, the following characteristic FT-IR
–
were at 74.6, 77.8 ppm. The obtained results showed that terminal al-
stretching peaks were found in HCPs-OH and MPAc-OH-Br an
–
– –
kynes have been successfully grafted into MPAc.
aliphatic C H vibration peak emanating from CH2 linkers at 2932
cmꢀ 1 and 2946 cmꢀ 1, respectively. Additionally, the characteristic FT-
IR stretching peaks of hydroxyl groups in HCPs-OH and MPAc-Br-OH
were found as a broad peak centered at about 3400 cmꢀ 1. The bands
MPAc-triazole-OH was synthesized by treating tri-alkyne MPAc with
an excess of 2-azido-1-phenylethanol (1.2 eq). The successful click re-
action between tri-alkyne MPAc and 2-azido-1-phenylethanol can also
be confirmed by 1H NMR spectroscopy (Fig. 5). The peaks at about 8.0
ppm are assigned to the proton of 1,2,3-triazole ring, and the signals
between 7.0 and 8.0 ppm are assigned to the protons of benzene rings. In
addition, the peaks between 0.50 and 2.00 ppm were assigned to the
protons of ternary phenanthrene ring structure of rosin.
at 1724 and 1726 cmꢀ 1 could be attributed to C O stretching of ester
–
–
groups in MPAc-OH and MPAc-OH-Br, respectively. Furthermore, the N
content of HCPs-OH and MPAc-Br-OH were determined to be 5.59% and
5.56% by using elemental analysis (EA), respectively. Obviously, the
results of FT-IR and EA suggested that most of MPAc-triazole-OH was
involved in the formation of the network.
The molecular structure of MPAc-triazole-OH was further verified by
using 13C NMR spectroscopy (Fig. 6). The peaks between
δ
=
In the 1H NMR spectrum of tri-alkyne MPAc (Fig. 3), the peaks be-
tween 0.55 and 1.90 ppm were assigned to the protons of rosin-based
ternary phenanthrene ring structure. The single peak at 2.42 ppm
160–180ppm represented the carbonyl carbons of ester groups. Eigh-
teen aromatic carbons are resonated between δ = 115–140ppm. The
6

S. Lai et al.
Reactive and Functional Polymers 165 (2021) 104976
100
80
60
40
20
0
a
b
100
200
300
400
500
600
700
800
Temperature ( C)
Fig. 7. TGA of MPAc-OH (a) and MPAc-OH-Br (b).
Adsorption
Desorption
a
(b)
300
200
100
0
3
Surface Area = 787 cm /
g
0.0
0.2
0.4
0.6
0.8
1.0
Relative Pressure (P/P0)
Fig. 8. SEM image (a) and N2 adsorption-desorption isotherm of MPAc-OH-Br (b).
2129 cmꢀ 1 suggests the complete transition from tri-alkyne MPAc to
MPAc-triazole-OH. In addition, the nitrogen content of MPAc-OH-Br
were found to be 5.56 wt% by elemental analysis. Clearly, the
–
peaks at δ = 140–150ppm confirmed the presence of the C C groups in
–
the 1,2,3-triazole ring. In addition, the FT-IR spectrum in Fig. 2c gives
the further evidence. The disappearance of the alkynyl absorption at
Table 1
Effect of different rosin-based polymeric catalysts catalyzed cyclization reaction between CO2 and 2-(prop-2-enoxymethyl)oxirane.a
Entry
Catalyst
Catalyst (mg)
TBABr (mmol)
Isolated yield (%)
1
2
3
4
5
6
7
8
9
None
0
0.1
0
26
31
69
46
76
48
90
61
99
HCPs
30
30
30
30
30
30
30
30
HCPs
0.1
0
HCPs-OH
HCPs-OH
MPAc-Br
MPAc-Br
MPAc-OH-Br
MPAc-OH-Br
0.1
0
0.1
0
0.1
Bold indicates the best catalytic result of rosin-based porous catalyst reported in this paper.
a
Reaction condition: 2-(phenoxymethyl)oxirane (10.0 mmol), CO2 (atmospheric pressure), 130 ◦C, 300 min.
7

S. Lai et al.
Reactive and Functional Polymers 165 (2021) 104976
weight loss is observed between 150 ◦C to 300 ◦C, which could be due to
the decomposition of the grafted n-butyl bromide. The obvious decrease
in the weight of MPAc-Br and MPAc-OH-Br in the temperature range of
300 ◦C to 800 ◦C is ascribed to the destruction of rosin skeleton in the
hyper-cross-linked porous polymer networks. The obtained results
indicated that MPAc-Br and MPAc-OH-Br could have potential appli-
cations in CO2 chemical transformation.
100
90
80
70
60
50
40
(a)
The morphology and surface characteristics of MPAc-OH-Br were
investigated by scanning electron microscope (SEM) and Bru-
nauer–Emmett–Teller (BET) N2 gas adsorption–desorption isotherms. As
shown in Fig. 8a, there were open and closed cells in the sample of
MPAc-OH-Br, which exhibited highly porous morphology. Furthermore,
the result of N2 gas sorption analysis further proved this fact and the BET
surface area of MPAc-OH-Br was 787 m3/g. According to Fig. 8b, the N2
adsorption isotherms told a sharply gas uptake at low relative pressure
(P/P0 < 0.01) and continuous increase at a high relative pressure (0.2 <
P/P0 < 1.0) with a hysteresis loop, which indicated that the rosin-base
MPAc-OH-Br was a multi-stage porous material with abundant micro-
pores and macropores structure.
Yield
70
80
90
100
110
120
130
Temperature (oC)
100
90
(b)
3.4. Effect of rosin-based porous catalysts on cyclic carbonate yields
The catalytic activity of the rosin-based porous catalysts was exam-
ined using CO2 and 2-(phenoxymethyl)oxirane as model reactants
(Table 1). The model reaction was carried out over two rosin-based
porous catalysts under 130 ◦C and atmospheric pressure conditions. As
expected, MPAc-OH-Br was found to exhibit excellent catalytic activity
for highly efficient synthesis of cyclic carbonates via chemical fixation of
CO2 with 2-(phenoxymethyl)oxirane under metal-, solvent-free and at-
mospheric pressure conditions, as illustrated in Table 1. When the re-
action was carried out using TBABr alone, the desired cyclic carbonate
yield was only 26% (entry 1, Table 1). When rosin-based catalyst was
used alone, the desired cyclic carbonate yield was very low or only
medium (31%–61%, entries 2, 4, 6, 8, Table 1). The combination of
HCPs and TBABr under the same reaction condition provided 69% yield.
The combination of MPAc-Br and TBABr provided 90% yield. To our
delight, the bifunctional catalyst MPAc-OH-Br (bearing triazole IL
80
70
Yield
10
15
20
25
30
Catalyst weight (mg)
–
groups and OH groups) showed excellent catalytic performance with a
100
90
80
70
60
50
(c)
yield of 99% owing to the molecularly cooperative effect among triazole
–
cations and OH groups. Since MPAc-OH-Br contains triazole IL groups
–
and OH groups, hydrogen bonds may play an important role in the
synergetic catalysis of the reaction. Based on these obtained results,
MPAc-OH-Br/TBABr was selected as the best catalytic system for further
investigations.
3.5. Optimization of cyclization reaction parameter
CO2 chemical conversion depends on the primary factors, such as
reaction temperature, catalyst amount, and reaction time of the reaction
system. Therefore, the influence of these reaction factors on the cyclo-
addition reaction was then examined, and the obtained results are
shown in Fig. 9. Fig. 9a shows the effect of reaction temperature on the
chemical fixation of CO2. The reaction temperature played an important
role in deciding the yield of cycloaddition reaction. The yields of
cycloaddition reaction increased rapidly from 53% to 99% when the
reaction temperature increased from 70 ◦C to 130 ◦C.
Yield
1
2
3
4
5
Time (h)
Fig. 9. Effect of reaction parameters on cyclic carbonate yield over MPAc-OH-
Fig. 9b shows the influence of catalytic amounts in the MPAc-OH-Br
mediated catalysis of CO2 and 2-(phenoxymethyl)oxirane cycloaddition.
It was found that cyclic carbonate yield was obviously increased when
increasing the amounts of MPAc-OH-Br from 10 mg to 30 mg. As illus-
trated in Fig. 9b, the yield of the desired cyclic carbonate reached the
maximum within 30 mg, up to 99%. At last, the effect of the reaction
time was examined while keeping other parameters (such as catalyst 30
Br: reaction temperature (a), catalyst amount (b), and reaction time (c).
obtained results showed that the benzene rings have been successfully
grafted into MPAc via CuAAC reaction.
The thermal stability of MPAc-OH and the catalyst MPAc-OH-Br was
analyzed by means of thermogravimetric analysis (TGA). As demon-
strated by TGA in a nitrogen atmosphere (Fig. 7), only slight weight loss
was observed below 150 ◦C, due to the removal of residual solvents and/
or adsorbed H2O. In the TGA plot of MPAc-OH-Br (Fig. 7b), about 15%
◦
mg, atmospheric pressure, and 130 C) constant in Fig. 9c. The yield
increased with reaction time and reached a maximum of 99% within
300 min. Up to now, the optimal reaction conditions for the chemical
8

S. Lai et al.
Reactive and Functional Polymers 165 (2021) 104976
Table 2
Cyclization reaction between CO2 and various epoxides under the optimized reaction condition.
Entrya
1
Substrate
Product
Isolated Yield (%)
88
2
3
99
92
4
5
95
96
6
99
7
8
9
93
91
88
10
11
96
68
aReaction conditions: epoxide (10.0 mmol), CO2 (atmospheric pressure), MPAc-OH-Br (30 mg), TBABr (0.1 mmol), 5 h.
9

S. Lai et al.
Reactive and Functional Polymers 165 (2021) 104976
100
80
60
40
20
0
99
99
99
98
100
98
98
98
98
96
96
b
a
80
60
40
20
0
100
200
300
400
Temp (oC)
500
600
700
800
Fig. 12. TGA of the fresh MPAc-OH-Br (a) and the recovered MPAc-OH-Br after
ten consecutive cycles (b).
1
2
3
4
5
6
7
8
9
10
Catalytic cycles
However, owing to the higher barrier height of ring opening, the yield of
corresponding product was only 68% (entry 11) when cyclohexene
oxide was used as the substrate in the same reaction conditions.
Fig. 10. Recyclability of MPAc-OH-Br under the optimal conditions.
3.7. Stability of MPAc-OH-Br
a
In order to develop a greener and more economical process for cyclic
carbonates synthesis, the reusability of MPAc-OH-Br was examined
under the optimal conditions in the following step. It was observed that
the MPAc-OH-Br catalyst exhibited good to excellent catalytic activity
for ten consecutive cycles, reflecting good stability of MPAc-OH-Br
(Fig. 10).
2931
1631
1725
3437
In the next step, the chemical and thermal stability of the recycled
MPAc-OH-Br after ten cycles were studied by FT-IR, EA and TGA anal-
ysis. The FT-IR of the reused MPAc-OH-Br catalyst was displayed in
Fig. 11. Compared with the fresh catalyst, after ten consecutive cycles,
the obtained catalyst still remains the characteristic peaks of MPAc
(1725 cmꢀ 1, ester functional groups) and hydroxyl groups (3400–3500
cmꢀ 1), which indicated that the skeleton structure of MPAc-OH-Br was
stable during catalytic reactions and after 10 times recycle. EA showed
that the N contents still well-preserved in the recovered MPAc-OH-Br,
still up to 4.91% (the fresh catalyst, 5.56%), which further testified
the outstanding chemical stability of MPAc-OH-Br. In addition, the
catalyst reused in ten consecutive runs was analyzed by TGA (Fig. 12b)
and showed a very similar TGA curves between 25 ◦C to 170 ◦C
compared to the fresh catalyst (Fig. 12a). These results indicate that the
catalyst MPAc-OH-Br has good stability. Thus, all of these results indi-
cate that the MPAc-OH-Br was a well-reusable and robust catalyst for the
chemical fixation CO2 with epoxides.
b
2931
3416
1725
1631
4000
3500
3000
2500
2000
1500
1000
500
Wavenumber (cm-1)
Fig. 11. FT-IR spectra of the fresh MPAc-OH-Br and the recovered MPAc-OH-Br
after ten consecutive cycles.
fixation of CO2 (atmospheric pressure) with epoxide (10.0 mmol) were
established as MPAc-OH-Br (30 mg) at 130 ◦C and 300 min reaction.
3.8. Possible reaction mechanism of the cycloaddition of CO2 with
epoxides
3.6. MPAc-OH-Br for chemical fixation of CO2 with other epoxides
To determine the potential applicability of the MPAc-OH-Br catalyst,
the substrate scope of cycloaddition reaction that involved epoxides
with different substituents was examined under the optimal reaction
conditions (130 ◦C, atmospheric pressure, 5 h). The detailed results are
summarized in Table 2. As shown in Table 2, high yields were achieved
for the mono-substituted terminal epoxides (Entries 1–11). All the ep-
oxides tested could be converted into the corresponding cyclic carbon-
ates with good to excellent yields. The steric effect may affect the yield.
For example, the reactive activity of the terminal epoxides decreased
with increasing their alkyl length (entries 4 and 5). Compared with
glycidol, epichlorohydrin showed a better result, probably due to the
electron-withdrawing property of the Cl atom (entries 6 and 7). In
addition, the epoxides with an oxymethylene moiety were also con-
verted to the corresponding products in excellent yields, indicating the
facilitated nucleophilic attack at the epoxide ring carbon atoms.
Based on the present results and previous published results [55,56], a
plausible mechanism was proposed for the chemical fixation epoxides
with CO2 over the MPAc-OH-Br catalyst (Scheme 3). MPAc-OH-Br with
–
OH functional groups demonstrated better catalytic activity, as the
–
OH functional groups might play a very important role in the activa-
tion of epoxides. Initially, the cycloaddition reaction is initiated by
–
activation of epoxy ring through hydrogen bonding of OH functional
groups on the surface of MPAc-OH-Br (I). Secondly, the nucleophilic Br
anion attacks the less-hindered carbon atom of the activated epoxide,
followed by the ring opening of the epoxy ring and formed the ring-
opened intermediate (II). Next, CO2 inserted into the intermediate and
an acyclic ester was obtained (III). In the final step (IV), the acyclic ester
was further converted to the corresponding cyclic carbonate through the
intramolecular ring-closure. At the same time, the catalyst MPAc-OH-Br
was regenerated. The excellent catalytic performance of MPAc-OH-Br
10

S. Lai et al.
Reactive and Functional Polymers 165 (2021) 104976
Br
HO
N
N
O
N
O
O
O
O
Br
N
O
N
O
NH
R
R
O
TBABr
OH
O
Br
N
N
O
Br
(IV)
N
OH
(I)
Br
HO
R
O
O
N
N
Br
O
(a)
Br
HO
N
O
N
N
Br
R
N
H
O
H
O
O
O
O
O
O
N
N
O
O
N
NH
N
Br
N
O
N
O
Br
N
N
O
O
N
O
H
Br
N
N
Br
O
O
O
(III)
H
Br
R
O
R
R
O
(c)
O
C
O
HO
Br
O C O
O
H
O
O
Br
N
N
N
(II)
Br
O
O
O
N
N
O
N
Br
N
O
N
N
O
Br
O
H
O
C
O
O
R
Br
Scheme 3. A plausible mechanism for the chemical fixation of CO2 with epoxides over MPAc-OH-Br.
can be attributed to the obvious cooperative effect of between –OH
heterogeneous catalysts, MPAc-OH-Br exhibited obvious advantages,
short reaction time (5 h), mild reaction condition (atmospheric pres-
sure), and excellent yield (99%) for the synthesis of cyclic carbonates.
functional groups and nucleophilic Br anions.
3.9. Comparison of MPAc-OH-Br with the reported heterogeneous
catalysts in the chemical fixation of CO2 with epoxides
Table 3
Comparison of catalytic performance of reported porous polymers.
Entry
Catalyst
Temp.
Time
(h)
Pressure
(MPa)
Yield
(%)
Ref.
(◦C)
To identify the potential of the rosin-based heterogeneous catalyst
MPAc-OH-Br for the preparation of cyclic carbonates, we have
compared the obtained result with previously reported catalytic systems
for cycloaddition of CO2 with epoxide. The result from our catalytic
system and the data from previously reported catalyst systems are
summarized in Table 3. As shown in Table 3, PIM2, IC2HCP-5, IHCP-OH
(1), BPyBr-ZnCl2/SiO2, PNPs-Im2ZnBr4, and PS-MimFeCl4 are examples
of catalysts which have been used for cycloaddition of CO2 with epoxide.
By comparing the previously reported results, it can be found that our
catalyst has higher catalytic activity. Obviously, the rosin-based porous
structure and the -OH groups on the surface of MPAc-OH-Br played an
important role to enhance catalytic activity. Compared with the existing
1
2
3
4
PIM2
130
120
135
120
8
1.0
3.0
3.0
1.7
96
92
90
88
[57]
[58]
[59]
[60]
IC2HCP-5
IHCP-OH (1)
BPyBr-
28
7
4
ZnCl2/SiO2
PNPs-
5
120
3.5
2.0
88
[61]
Im2ZnBr4
PS-MimFeCl4
MPAc-OH-Br
6
100
6
8
96
[62]
This
work
7
130
5
Balloon
>99
Bold indicates the best catalytic result of rosin-based porous catalyst reported in
this paper.
11

S. Lai et al.
Reactive and Functional Polymers 165 (2021) 104976
[14] Y.R. Wang, L.Y. Guo, L.Z. Yin, Progress in the heterogeneous catalytic cyclization
of CO2 with epoxides using immobilized ionic liquids, Catal. Lett. 149 (2019)
985–997, https://doi.org/10.1007/s10562-019-02669-y.
4. Conclusions
In summary, a class of biomass-derived bifunctional porous hetero-
[15] A.J. Kamphuis, F. Picchioni, P.P. Pescarmona, CO2-fixation into cyclic and
polymeric carbonates: principles and applications, Green Chem. 21 (2019)
406–448, https://doi.org/10.1039/C8GC03086C.
–
geneous catalyst MPAc-OH-Br (bearing triazole IL groups and OH
groups), based on easily available and sustainable rosin, was synthesized
by Friedel–Crafts polymerization and the further N-alkylation of triazole
groups. The synthesized rosin-based polymeric monomers and the
MPAc-OH-Br catalyst was thoroughly characterized by different tech-
niques, such as FT-IR, 1H NMR, 13C NMR, TGA, SEM, and BET.
[16] P. Bhanja, A. Modak, A. Bhaumik, Porous organic polymers for CO2 storage and
conversion reactions, ChemCatChem 11 (2019) 244–257, https://doi.org/
10.1002/cctc.201801046.
[17] S. Wang, C.J. Xi, Recent advances in nucleophile-triggered CO2-incorporated
cyclization leading to heterocycles, Chem. Soc. Rev. 48 (2019) 382–404, https://
doi.org/10.1039/C8CS00281A.
Compared with MPAc-Br, bifunctional MPAc-OH-Br displayed
a
[18] G. Zhao, X. Huang, X. Wang, X. Wang, Progress in catalyst exploration for
heterogeneous CO2 reduction and utilization: a critical review, J. Mater. Chem. A 5
(2017) 21625–21649, https://doi.org/10.1039/C7TA07290B.
remarkable catalytic activity for chemical fixation of CO2 with epoxides
into cyclic carbonates (up to 99% yields) under metal-, solvent-free and
atmospheric pressure conditions (130 ◦C, 5 h). In addition, MPAc-OH-Br
exhibited good stability and reusability (96% yield after 10 recycles).
The present study demonstrated that the rosin-based porous molecular
structure and bifunctional groups on the surface of MPAc-OH-Br played
a very important role to enhance its catalytic activity.
[19] S.N. Habisreutinger, L. Schmidt-Mende, J.K. Stolarczyk, Photocatalytic reduction
of CO2 on TiO2 and other semiconductors, Angew. Chem. Int. Ed. 52 (2013)
7372–7408, https://doi.org/10.1002/anie.201207199.
[20] S. Zeng, X. Zhang, L. Bai, X. Zhang, H. Wang, J. Wang, D. Bao, M. Li, X. Liu,
S. Zhang, Ionic-liquid-based CO2 capture systems: structure, interaction and
process, Chem. Rev. 117 (2017) 9625–9673, https://doi.org/10.1021/acs.
chemrev.7b00072.
[21] M. Liu, L. Liang, X. Li, X. Gao, J. Sun, Novel urea derivative based ionic liquids with
dual-functions: CO2 capture and conversion under metal- and solvent-free
conditions, Green Chem. 18 (2016) 2851–2863, https://doi.org/10.1039/
C5GC02605A.
Declaration of Competing Interest
None.
[22] L.W. Sun, J.Y. Luo, M. Gao, S.K. Tang, Bi-functionalized ionic liquid porous
copolymers for CO2 adsorption and conversion under ambient pressure, React.
Funct. Polym. 154 (2020) 104636, https://doi.org/10.1016/j.
reactfunctpolym.2020.104636.
Acknowledgments
[23] Y. Liu, Y. Song, J.H. Zhou, X.P. Zhang, Modified polyether glycols supported ionic
liquids for CO2 adsorption and chemical fixation, Mol. Catal. 492 (2020) 111008,
https://doi.org/10.1016/j.mcat.2020.111008.
This work was financially supported by the National Natural Science
Foundation of China (21004024), the Natural Science Foundation of
Fujian Province (2016J01063), the Program for New Century Excellent
Talents in University of Fujian Province (2012FJ-NCET-ZR03) and the
Subsidized Project for Postgraduates’ Innovative Fund in Scientific
Research of Huaqiao University.
[24] S. Suleman, H.A. Younus, N. Ahmad, Z.A.K. Khattak, H. Ullah, J. Park, T. Han, B.
J. Yu, F. Verpoort, Triazole based cobalt catalyst for CO2 insertion into epoxide at
ambient pressure, Appl. Catal. A 591 (2020) 117384, https://doi.org/10.1016/j.
apcata.2019.117384.
[25] Q. Zhang, P. Yu, B. Lei, H.J. Yang, J.C. Hu, L.H. Wang, T.F. Zhou, Q.Q. Jiang, J.
J. Zhu, B.X. Han, Efficient solvent-free synthesis of cyclic carbonates from the
cycloaddition of carbon dioxide and epoxides catalyzed by new imidazolinium
functionalized metal complexes under 0.1 MPa, Catal. Lett. 150 (2020)
2537–2548, https://doi.org/10.1007/s10562-020-03163-6.
References
[26] G.J. Chen, Y.D. Zhang, J.Y. Xu, X.Q. Liu, K. Liu, M.M. Tong, Z.Y. Long,
Imidazolium-based ionic porous hybrid polymers with POSS-derived silanols for
efficient heterogeneous catalytic CO2 conversion under mild conditions, Chem.
Eng. J. 381 (2020) 122765, https://doi.org/10.1016/j.cej.2019.122765.
[27] S.S. Dhankhar, C.M. Nagaraja, Porous nitrogen-rich covalent organic framework
for capture and conversion of CO2 at atmospheric pressure conditions, Micropor.
Mesopor. Mat. 308 (2020) 110314, https://doi.org/10.1016/j.
[1] J.L. Schnoor, Ocean acidification: the other problem with CO2, Environ. Sci.
Technol. 48 (2014) 10529–10530, https://doi.org/10.1021/es503107u.
[2] D.A. Lashof, D.-R. Ahuja, Relative contributions of greenhouse gas emissions to
global warming, Nature 344 (1990) 529–531, https://doi.org/10.1038/344529a0.
[3] J. Artz, T.E. Müller, K. Thenert, Sustainable conversion of carbon dioxide: an
integrated review of catalysis and life cycle assessment, Chem. Rev. 118 (2018)
434–504, https://doi.org/10.1021/acs.chemrev.7b00435.
micromeso.2020.110314.
[28] Z.L. Shi, J.C. Jiao, Q.X. Han, Y. Xiao, L.K. Huang, M.X. Li, Synthesis Cu(I)-CN-based
MOF with in-situ generated cyano group by cleavage of acetonitrile: highly
efficient for catalytic cyclization of propargylic alcohols with CO2, Mol. Catal. 496
(2020) 111190, https://doi.org/10.1016/j.mcat.2020.111190.
[4] Y. Zhou, W.L. Zhang, L. Ma, Y. Zhou, J. Wang, Amino acid anion paired
mesoporous poly(ionic liquid)s as metal/halogen-free heterogeneous catalysts for
carbon dioxide fixation, ACS Sustain. Chem. Eng. 7 (2019) 9387–9398, https://doi.
org/10.1021/acssuschemeng.9b00591.
[29] Y.P. Wang, J.Q. Nie, C.F. Lu, F.Y. Wang, C. Ma, Z.X. Chen, G.C. Yang, Imidazolium-
based polymeric ionic liquids for heterogeneous catalytic conversion of CO2 into
cyclic carbonates, Micropor. Mesopor. Mat. 292 (2020) 109751, https://doi.org/
10.1016/j.micromeso.2019.109751.
[5] Z.J. Guo, Q.W. Jiang, Y.M. Shi, J. Li, X.N. Yang, W. Hou, Y. Zhou, J. Wang,
Tethering dual hydroxyls into mesoporous poly(ionic liquid)s for chemical fixation
of CO2 at ambient conditions: a combined experimental and theoretical study, ACS
Catal. 7 (2017) 6770–6780, https://doi.org/10.1021/acscatal.7b02399.
[6] J. Li, D.G. Jia, Z.J. Guo, Y.Q. Liu, Y.N. Lyu, Y. Zhou, J. Wang, Imidazolinium-based
porous hypercrosslinked ionic polymers for efficient CO2 capture and fixation with
epoxides, Green Chem. 19 (2017) 2675–2686, https://doi.org/10.1039/
C7GC00105C.
[30] B.B. Gu, T. Xu, G.R. Xu, J. Bai, C.P. Li, Synthesis of styrene carbonate from styrene
and CO2 catalyzed by walnut-like zeolite LZ-276, Micropor. Mesopor. Mat. 293
(2020) 109779, https://doi.org/10.1016/j.micromeso.2019.109779.
[31] M. Cipriana, K.H. Ruiza, M. Kassymova, T.T. Wang, S. Zhuiykov, S. Chaemchuen,
R. Tu, F. Verpoort, 3D derived N-doped carbon matrix from 2D ZIF-L as an
enhanced stable catalyst for chemical fixation, Micropor. Mesopor. Mat. 285
(2019) 80, https://doi.org/10.1016/j.micromeso.2019.04.053.
[7] M. Aresta, A. Dibenedetto, A. Angelini, Catalysis for the valorization of exhaust
carbon: from CO2 to chemicals, materials, and fuels. Technological use of CO2,
Chem. Rev. 114 (2014) 1709–1742, https://doi.org/10.1021/cr4002758.
[8] R. Babu, A.C. Kathalikkattil, R. Roshan, J. Tharun, D. Kimb, D. Park, Dual-porous
metal organic framework for room temperature CO2 fixation via cyclic carbonate
synthesis, Green Chem. 18 (2016) 232–242, https://doi.org/10.1039/
C5GC01763G.
´
[32] L.C. St’astna, A. Krupkova, R. Petrickovic, M. Mullerova, J. Matousek, K. Kostejn,
P. Curinova, V. Jandova, S. Sabata, T. Strasak, Multivalent bifunctional carbosilane
dendrimer-supported ammonium and phosphonium organocatalysts for the
coupling of CO2 and epoxides, ACS Sustain. Chem. Eng. 8 (2020) 11692–11703,
https://doi.org/10.1021/acssuschemeng.0c03367.
[9] J. Liang, Y. Xie, Q. Wu, X. Wang, T. Liu, H. Li, Y. Huang, R. Cao, Zinc porphyrin/
imidazolium integrated multivariate zirconium metal–organic frameworks for
transformation of CO2 into cyclic carbonates, Inorg. Chem. 57 (2018) 2584–2593,
https://doi.org/10.1021/acs.inorgchem.7b02983.
[33] M.K. Alavijeh, M.M. Amini, B. Notash, G. Mohammadnezhad, Formation of a
potassium coordination polymer based on a novel 2-sulfono-benzene-1,3,5-tricar-
boxylic acid: synthesis, characterization, and application of the organocatalyst in
CO2 cycloaddition reaction, J. Mol. Struct. 1232 (2021) 130045, https://doi.org/
10.1016/j.molstruc.2021.130045.
[10] J. Chen, M. Zhong, L. Tao, L. Liu, S. Jayakumar, C. Li, H. Li, Q. Yang, The
cooperation of porphyrin-based porous polymer and thermal-responsive ionic
liquid for efficient CO2 cycloaddition reaction, Green Chem. 20 (2018) 903–911,
https://doi.org/10.1039/C7GC03801A.
[34] A.-I. Adeleyea, S. Kellici, T. Heil, D. Morgan, M. Vickers, B. Saha, Greener synthesis
of propylene carbonate using graphene-inorganic nanocomposite catalysts, Catal.
Today 256 (2015) 347–357, https://doi.org/10.1016/j.cattod.2014.12.032.
[35] L.L. Hu, Q.J. Xie, J.T. Tang, C.Y. Pan, G.P. Yu, K.C. Tam, Co(III)-Salen immobilized
cellulose nanocrystals for efficient catalytic CO2 fixation into cyclic carbonates
under mild conditions, Carbohydr. Polym. 256 (2021) 117558, https://doi.org/
10.1016/j.carbpol.2020.117558.
´
´
[11] A. Tortajada, F. Julia-Hernandez, M. Bçrjesson, T. Moragas, R. Martin, Transition-
metal-catalyzed carboxylation reactions with carbon dioxide, Angew. Chem. Int.
Ed. 57 (2018) 15948–15982, https://doi.org/10.1002/anie.201803186.
[12] H. Seo, L.V. Nguyen, T.F. Jamison, Using carbon dioxide as a building block in
continuous flow synthesis, Adv. Synth. Catal. 361 (2019) 247–264, https://doi.
org/10.1002/adsc.201801228.
´
[36] C. Claver, M.B. Yeamin, M. Regueroa, A.M. Masdeu-Bulto, Recent advances in the
use of catalysts based on natural products for the conversion of CO2 into cyclic
carbonates, Green Chem. 22 (2020) 7665–7706, https://doi.org/10.1039/
D0GC01870H.
[13] S. Dabral, T. Schaub, The use of carbon dioxide (CO2) as a building block in organic
synthesis from an industrial perspective, Adv. Synth. Catal. 361 (2019) 223–246,
https://doi.org/10.1002/adsc.201801215.
12

S. Lai et al.
Reactive and Functional Polymers 165 (2021) 104976
[37] L.P. Guo, K.J. Lamb, M. North, Recent developments in organocatalyzed
transformations of epoxides and carbon dioxide into cyclic carbonates, Green
Chem. 23 (2021) 77–118, https://doi.org/10.1039/D0GC03465G.
[50] Z. Wang, M.S. Ganewatta, C. Tang, Sustainable polymers from biomass: bridging
chemistry with materials and processing, Prog. Polym. Sci. 101 (2020) 101197,
https://doi.org/10.1016/j.progpolymsci.2019.101197.
[38] A. Chinnappan, A.H. Tamboli, W.J. Chung, H. Kim, Green synthesis,
characterization and catalytic efficiency of hypercross-linked porous polymeric
ionic liquid networks towards 4-nitrophenol reduction, Chem. Eng. J. 285 (2016)
554–561, https://doi.org/10.1016/j.cej.2015.10.032.
[51] X.Q. Xiong, H. Zhang, S.L. Lai, J.B. Gao, L.Z. Gao, Lignin modified by deep eutectic
solvents as green, reusable, and bio-based catalysts for efficient chemical fixation
of CO2, React. Funct. Polym. 149 (2020) 104502, https://doi.org/10.1016/j.
reactfunctpolym.2020.104502.
[39] Z.H. Hei, G.L. Song, C.Y. Zhao, W.H. Fan, M.H. Huang, Supramolecular porous
ionic network based on triazinonide and imidazolium: a template-free synthesis of
meso-/macroporous organic materials via a one-pot reaction-assembly procedure,
RSC Adv. 6 (2016) 92443–92448, https://doi.org/10.1039/C6RA20590A.
[52] S.L. Lai, J.B. Gao, H. Zhang, L. Cheng, X.Q. Xiong, Luffa sponge supported dendritic
imidazolium ILs with high-density active sites as highly efficient and
environmentally friendly catalysts for CO2 chemical fixation, J. CO2 Util. 38
(2020) 148–157, https://doi.org/10.1016/j.jcou.2020.01.004.
[53] J.S. Lee, S.I. Hong, Synthesis of acrylic rosin derivatives and application as
negative photoresist, Eur. Polym. J. 28 (2002) 387–392, https://doi.org/10.1016/
S0014-3057(00)00204-4.
¨
[40] K. Tauber, A. Dani, J. Yuan, Covalent cross-linking of porous poly(ionic liquid)
membrane via a triazine network, ACS Macro Lett. 6 (2017) 1–5, https://doi.org/
10.1021/acsmacrolett.6b00782.
[41] S. Li, Z. Chen, X.C. Ling, J.J. Cao, Q. Wang, Y. Zhou, J. Wang, Engineering
polyoxometalate anions on porous ionic network towards highly catalytic active
noble metal clusters, Appl. Surf. Sci. 496 (2019) 143650, https://doi.org/10.1016/
j.apsusc.2019.143650.
[54] X. Liu, W. Xin, J. Zhang, Rosin-based acid anhydrides as alternatives to
petrochemical curing agents, Green Chem. 11 (2009) 1018–1025, https://doi.org/
10.1039/B903955D.
´
[55] J.A. Castro-Osma, J. Martínez, F. Cruz-Martínez, M.P. Caballero, J. Fernandez-
´
´
[42] Y. Zhi, P. Shao, X. Feng, H. Xia, Y. Zhang, Z. Shi, Y. Mu, X. Liu, Covalent organic
frameworks: efficient, metal-free, heterogeneous organocatalysts for chemical
fixation of CO2 under mild conditions, J. Mater. Chem. A 6 (2018) 374–382,
https://doi.org/10.1039/C7TA07691F.
Baeza, J. Rodríguez-Lopez, A. Otero, A. Lara-Sanchez, J. Tejeda, Development of
hydroxy-containing imidazole organocatalysts for CO2 fixation into cyclic
carbonates, Catal. Sci. Technol. 8 (2018) 1981–1987, https://doi.org/10.1039/
C8CY00381E.
[43] Z.W. Liu, B.H. Han, Ionic porous organic polymers for CO2 capture and conversion,
Curr. Opin. Green Sustain. Chem. 16 (2019) 20–25, https://doi.org/10.1016/j.
cogsc.2018.11.008.
[56] Y. Wang, S. Li, Y. Yang, X. Shen, H. Liu, B. Han, A fully heterogeneous catalyst Br-
LDH for the cycloaddition reactions of CO2 with epoxides, Chem. Commun. 55
(2019) 6942–6945, https://doi.org/10.1039/C9CC03052B.
[44] Y.Q. Wang, J. Nie, C. Lu, F. Wang, C. Ma, Z. Chen, G. Yang, Imidazolium-based
polymeric ionic liquids for heterogeneous catalytic conversion of CO2 into cyclic
carbonates, Micropor. Mesopor. Mat. 292 (2020) 109751, https://doi.org/
10.1016/j.micromeso.2019.109751.
[57] Y.P. Wang, N.Q. Nie, C.F. Lu, F.Y. Wang, C. Ma, Z.X. Chen, G.C. Yang,
Imidazolium-based polymeric ionic liquids for heterogeneous catalytic conversion
of CO2 into cyclic carbonates, Micropor. Mesopor. Mat. 292 (2020) 109751,
https://doi.org/10.1016/j.micromeso.2019.109751.
[45] Y. Zhang, K. Liu, L. Wu, H. Zhong, N. Luo, Y. Zhu, M. Tong, Z. Long, G. Chen,
Silanol-enriched viologen-based ionic porous hybrid polymers for efficient
catalytic CO2 fixation into cyclic carbonates under mild conditions, ACS Sustain.
Chem. Eng. 7 (2019) 16907–16916, https://doi.org/10.1021/
acssuschemeng.9b04627.
[58] W.L. Zhang, F.P. Ma, L. Ma, Y. Zhou, J. Wang, Imidazolium-functionalized ionic
hypercrosslinked porous polymers for efficient synthesis of cyclic carbonates from
simulated flue gas, ChemSusChem 13 (2020) 341–350, https://doi.org/10.1002/
cssc.201902952.
[59] D.G. Jia, L. Ma, Y. Wang, W.L. Zhang, J. Li, Y. Zhou, J. Wang, Efficient CO2
enrichment and fixation by engineering micropores of multifunctional
hypercrosslinked ionic polymers, Chem. Eng. J. 390 (2020) 124652, https://doi.
org/10.1016/j.cej.2020.124652.
[46] Y. Xie, J. Liang, Y. Fu, J. Lin, H. Wang, S. Tu, J. Li, Poly(ionic liquid)s with high
density of nucleophile/electrophile for CO2 fixation to cyclic carbonates at mild
conditions, J. CO2 Util. 32 (2019) 281–289, https://doi.org/10.1016/j.
jcou.2019.04.023.
[60] M.I. Kim, S.J. Choi, D.W. Kim, D.W. Park, Catalytic performance of zinc containing
ionic liquids immobilized on silica for the synthesis of cyclic carbonates, J. Ind.
Eng. Chem. 20 (2014) 3102–3107, https://doi.org/10.1016/j.jiec.2013.11.051.
[61] P. Mao, W.L. Dai, W.Y. Yang, S.L. Luo, Y. Zhang, J. Mao, X.B. Luo, J.P. Zou,
Polymer nanoparticles grafted zinc-containing ionic liquids: a highly efficient and
recyclable catalyst for cooperative cycloaddition of CO2 with epoxides, J. CO2 Util.
28 (2018) 96–106, https://doi.org/10.1016/j.jcou.2018.09.017.
[47] E.M. Maya, E. Verde-Sesto, D. Mantione, M. Iglesias, D. Mecerreyes, New poly
(ionic liquid)s based on poly(azomethine-pyridinium) salts and its use as
heterogeneous catalysts for CO2 conversion, Eur. Polym. J. 110 (2019) 107–113,
https://doi.org/10.1016/j.eurpolymj.2018.07.030.
[48] Y.Q. Zhu, C. Romain, C.K. Williams, Sustainable polymers from renewable
resources, Nature 540 (2016) 354–362, https://doi.org/10.1038/nature21001.
[49] P.A. Wilbon, F. Chu, C. Tang, Progress in renewable polymers from natural
terpenes, terpenoids, and rosin, Macromol. Rapid Comm. 34 (2013) 8–37, https://
doi.org/10.1002/marc.201200513.
[62] J. Gao, Q.W. Song, L.N. He, C. Liu, Z.Z. Yang, X. Han, X.D. Li, Q.C. Song,
Preparation of polystyrene-supported Lewis acidic Fe(III) ionic liquid and its
application in catalytic conversion of carbon dioxide, Tetrahedron 68 (2012)
3835–3842, https://doi.org/10.1016/j.tet.2012.03.048.
13