Triazine-based Organic Polymer-catalysed Conversion of Epoxide to Cyclic Carbonate under Ambient CO2 Pressure

Article abstract of DOI:10.1002/asia.201901277

In this work we have achieved epoxide to cyclic carbonate conversion using a metal-free polymeric catalyst under ambient CO₂ pressure (1.02 atm) using a balloon setup. The triazine containing polymer (CYA-ANIS) was prepared from cyanuric chloride (CYA?Cl) and o-dianisidine (ANIS) in anhydrous DMF as solvent by refluxing under the N₂ gas environment. The presence of triazine and amine functional groups in the polymer results in the adsorption of CO₂ up to 7 cc/g at 273 K. This inspired us to utilize the polymer for the conversion of a series of functionalised epoxides into their corresponding cyclic carbonates in the presence of tetrabutyl ammonium iodide (TBAI) as co-catalyst. The product has wide range of applications like solvent in lithium ion battery, precursor for polycarbonate, etc. The catalyst was efficient for the conversion of different mono and di-epoxides into their corresponding cyclic carbonates under atmospheric pressure in the presence of TBAI as co-catalyst. The study indicates that epoxide attached with electron withdrawing groups (like, CH₂Cl, glycidyl ether, etc.) displayed better conversion compared to simple alkane chain attached epoxides. This is mainly due to the stabilization of electron rich intermediates produced during the reaction (e. g. epoxide ring opening or CO₂ incorporation into the halo-alkoxide anion). This catalyst mixture was capable to maintain its reactivity up to five cycles without losing its activity. Post catalytic characterization clearly supports the heterogeneous and recyclable nature of the catalyst.

Full text of DOI:10.1002/asia.201901277

CHEMISTRY
AN ASIAN JOURNAL
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Accepted Article
Title: A triazine-based porous organic polymer catalysed epoxide to
cyclic carbonate conversion under ambient CO2 pressure
Authors: Venkataramanan Mahalingam, Tanmoy Biswas, Arjun Halder,
Khusboo Shivdas Paliwal, Gouri Tudu, Antarip Mitra, and
Rahul Banerjee
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10.1002/asia.201901277
Chemistry - An Asian Journal
COMMUNICATION
A triazine-based organic polymer catalysed epoxide to cyclic
carbonate conversion under ambient CO2 pressure
Tanmoy Biswas,[a] ArjunHalder,[b] Khusboo S. Paliwal,[a] Antarip Mitra,[a] Gouri Tudu,[a] Rahul
Banerjee[a],[c] and Venkataramanan Mahalingam*[a]
Abstract: In this work we have achieved epoxide to cyclic carbonate
conversion using a metal-free polymeric catalyst under ambient CO2
pressure (1.02 atm) using a balloon setup. The triazine containing
polymer (CYA-ANIS) was prepared from cyanuric chloride (CYA-Cl)
and o-dianisidine (ANIS) in anhydrous DMF as solvent by refluxing
under the N2 gas environment. The presence of triazine and amine
functional groups in the polymer results in the adsorption of CO2 up
to 7 cc/g at 273 K. This inspired us to utilize the polymer for the
technologies which are capable of separating CO2 from
atmosphere.3 Thus, developing strategies to convert them into
value-added chemicals or fuels is important and very essential.
Epoxide to cyclic carbonate conversion in the presence of CO2 is
one of the solution for CO2 utilization due to the wide likehighly
polar aprotic and high boiling solvent, preparation of methanol,
solvent for lithium ion battery, monomer for polycarbonates, etc.4
Industrial method for cyclic carbonate preparation requires the
use of corrosive chemical i.e. phosgene and as a result
hydrogen chloride is produced as a by-product.5 Although there
are quite a few reports on the preparation of cyclic carbonate
using epoxide and CO2, most of them use high pressure (5-50
atm). In addition, there are quite a few reports where use of
homogeneous catalyst has been reported, which introduces
additional difficulty during the catalyst separation from reaction
mixture.6
The major problem associated with the CO2 fixation is the high
thermodynamic stability and kinetic inertness of the CO2
molecule itself.7 Additionally, the solubility of CO2 in commonly
used organic solvents is very low which makes the CO2 fixation
further difficult. To achieve effective CO2 adsorption, functional
groups like amine, imine, guanidine, pyridine, triazine, imidazole,
etc. are already proven to be effective and this is extremely
important criteria for catalytic CO2 conversion into useful
chemical.8,9 For example, Liu and co-worker reported an o-
hydroxyazobenzene containing mesoporous polymer which was
capable to bring about the same conversion under 30 atm
pressures and in the presence of tertrabutyl ammonium bromide
(TBAB) co-catalyst.10 In addition, Thomas et al. reported
polymeric triazine based materials which were capable to
convert epoxide into cyclic carbonate under high pressure.11 In
this direction, Liu et al. reported hydrazine containing triazine-
based polymer for epoxide to cyclic carbonate conversion under
10 atm pressure.12 Most of the above reports use high CO2
pressure for the conversion. To our knowledge there are few
reports where this conversion is reported at ambient pressure.13
For example, porphyrin containing and triazine-urea containing
polymers have found to be efficient for the epoxides conversion
using CO2 under 1 atm pressure in the presence of TBAB as co-
catalyst.14 Likewise, Zhi et al. reported triazine containing
covalent organic framework (COF) which achieved the catalytic
conversion of epoxides to cyclic carbonate under atmospheric
pressure along with TBAB as co-catalyst.15 In parallel, Ravi and
co-workers reported an hydroxylamine-anchored COF which
showed conversion of differently functionalized epoxides under 1
atm pressure in the presence of quaternary ammonium iodide.9
The major difficulty of COF is associated with the scalability.
Moreover, multiple steps for synthesis of monomer introduce
additional cost and time to the catalyst preparation. These
motivated us to prepare the triazine containing polymeric
organicmaterial in one step from commercially available and
cheap synthons with gram scale preparation which can be
efficient for both CO2 adsorption as well as epoxide to cyclic
conversion of
a series of functionalised epoxides into their
corresponding cyclic carbonates in the presence of tetrabutyl
ammonium iodide (TBAI) as co-catalyst.The resulting products have
wide range of applications like solvent in lithium ion battery,
precursor for polycarbonate, etc. The catalyst was efficient for the
conversion of different mono and di-epoxides into their
corresponding cyclic carbonates under atmospheric pressure in the
presence of tetrabutyl ammonium iodide TBAI as co-catalyst. The
study indicates that epoxide attached with electron withdrawing
groups (like, CH2Cl, glycidyl ether, etc.) displayed better conversion
compared to simple alkane chain attached epoxides. This is mainly
due to the stabilization of electron rich intermediates produced
during the reaction (e.g. epoxide ring opening or CO2 incorporation
into the halo-alkoxide anion). This catalyst mixture was capable to
maintain its reactivity up to five cycles without losing its activity. Post
catalytic characterization clearly supports the heterogeneous and
recyclable nature of the catalyst.
Global warming and climate change are serious threat for
climate security of earth. This is mainly due to the increase in
the CO2 concentration in the atmosphere caused by the massive
deforestation and excessive consumption of fossil fuels for our
day-to-day life. More precisely, it has risen from 280 ppm before
the industrial revolution to 410 ppm today and it is expected to
reach 2000 ppm by AD 2250.1 This massive change may bring
about analarming elevation in sea water level and temperature
ofthe massive water bodies as well as the atmosphere. This may
result in the capture of many useful lands and may destroy many
temperature sensitive marine ecosystems. It is essential to
utilize the excess CO2 in the atmosphere to develop sustainable
methods to convert them into value added chemicals by utilizing
it as a C1 feedstock.2 In fact, scientists have already developed
[a]
Dr. T. Biswas, Dr. V. Mahalingam, Dr. R. Banerjee, K. Paliwal ,
A. Mitra, G. Tudu, Department of Chemical Sciences, Indian
Institute of Science Education and Research (IISER) Mohanpur,
Kolkata, West Bengal 741252, India. E-mail:
mvenkataramanan@yahoo.com; Fax: 91-33-25873020;
Tel: +91(0)9007603474.
[b]
[c]
Dr. A. Halder, Department of Chemistry, University of California,
Berkeley, California 94720, United States
Dr. R. Banerjee, Physical/Materials Chemistry Division and
Academy of Scientific and Innovative Research (AcSIR), CSIR-
National Chemical Laboratory (CSIR-NCL) Pune 411008 (India)
Electronic Supplementary Information (ESI) available: [PXRD,
FT-IR, TGA, FESEM, TEM, Balloon pressure measurement, all
the NMR spectra measurement, mechanistic cycle for co-
catalyst-free epoxide to cyclic carbonate conversion and
recyclability]. See DOI: 10.1039/x0xx00000x.
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carbonate conversion under atmospheric pressure as
a
absence of any catalyst the reactant showed no conversion
(Table 1, entry 1). However, in the presence of 50 mg of catalyst
it showed only 45% conversion (Table 1, entry 2). Increasing the
catalyst amount to 100 mg increases the conversion up to 70%
(Table 1, entry 3). We believe the N-H bond is performing the
role as hydrogen bond donor for epoxide activation and nitrogen
atom of the triazine ring is acting as nucleophilic center for the
opening up of the three member epoxide ring [Fig. ESI 23]. In
fact, the reactivity of the CYA-ANIS as catalyst is comparatively
better than the well-known nitrogen rich, triazine containing,
metal-free 2D polymeric material (poly-triazine) reported by
Roser and co-worker.9a This clearly supports the better reactivity
of CYA-ANIS due to the presence of more number of hydrogen
bond donor sites for epoxide activation. Furthermore, the
complete conversion was achieved when 1.67 mol% TBAI was
used as co-catalyst (Table 1, entry 5). In fact, the use of co-
catalyst alone contributes only to 15% conversion of
epichlorohydrin to its corresponding cyclic carbonate (Table 1,
entry 4). These results clearly suggest the co-operative or
synergistic reactivity of the catalyst and co-catalyst for the cyclic
carbonate conversion. Decreasing the reaction time from 20 h to
12 h reduces the conversion efficiency to 80% (Table 1, entry 6).
Similarly, a decrease in the conversion (72%) was observed
when the reaction temperature was reduced to 85°C from 105°C
(Table 1, entry 7). The above observations suggest that use of
100 mg catalyst and 1.67 mol% of co-catalyst respectively at
105°C for 20h was considered as the optimum condition for this
reaction and utilized for the conversion of other functionalized
epoxides into their corresponding cyclic carbonates.
heterogeneous catalyst.
Scheme. 1: The synthetic protocol for the preparation of CYA-ANIS
polymer.
In this work, we have prepared a traizine containing polymer
from cyanuric chloride and o-dianisidine in the presence of
anhydrous N.N-dimethyl formamide (DMF) as solvent (Scheme.
1). This resulting material was found to be active for the
conversion of a wide range of epoxides to their corresponding
cyclic carbonates under atmospheric pressure in the presence of
TBAI as co-catalyst.
The prepared catalyst material was characterized using 13C CP-
MAS, PXRD, FT-IR, TGA, SEM, TEM and BET. From 13C CP-
MAS analysis it was observed that the peak corresponding to
the aromatic region was appeared between 110-130 ppm (Fig.
1). Whereas the peaks for triazine, imine and methyl carbon
were observed at 160 ppm, 147 ppm and 54 ppm, respectively.
All the peak positions were verified with the monomer
prepared.The thermal stability of the polymer was noted from
TGA analysis. It was observed that the material contains 20 wt%
of adsorbed moisture or solvent molecules. Additional 40%
weight loss was noted between 300-400oC [Fig. ESI 1(a)]. The
PXRD analysis revealed that the polymer is amorphous in
nature [Fig. ESI 1(b)]. Additionally, the polymer did not exhibit
any particular morphology which was observed in SEM [Fig. ESI
1(c)] and the 2D sheet like nature of the catalyst was verified in
TEM analysis [Fig. ESI 1(d)]. The surface area of CYA-ANIS
was observed to be 3 m2/g and H3 hysteresis type IV loop was
obtained from BET analysis which is understood better from the
zoomed version of the highlighted area [Fig. ESI 2(a) and 2(b)].
In addition, the polymer is capable to adsorb 7 cc/g of CO2 at
273 K temperature [Fig. ESI 3]. This CO2 adsorption efficiency
inspired us to check its catalytic efficiency for CO2 conversion of
epoxides into cyclic carbonates.
Table 1: Optimization of reaction conditions for catalytic
CO2 fixation with epichlorohydrin.
Entry
Catalyst
Amount of
Catalyst
--
50 mg
100 mg
1.67 mol%
100 mg + 1.67
mol %
Condition
Temp. & Time
105°C, 20 h
105°C, 20 h
105°C, 20 h
105°C, 20 h
105°C, 20 h
Conversion
(%)
0
45
70
15
100
1
2
3
4
5
No Catalyst
CYA-ANIS
CYA-ANIS
TBAI
CYA-ANIS
+ TBAI
6
7
CYA-ANIS
+ TBAI
CYA-ANIS
+ TBAI
100 mg + 1.67
mol %
100 mg + 1.67
mol %
105°C, 12 h
85°C, 20 h
80
72
Condition: substrate,epichlorohydrin 15 mmol, CO2 gas [balloon, 99.5%
pure, pressure 1.02 atm9c product conversion was measured using 1H
NMR spectroscopy.
The catalyst mixture CYA-ANIS was tested for a wide variety of
substrates under the optimum conditions. It was noted that along
with epichlorihydrin, styrene oxide and other terminal glycidyl
ethers displayed almost complete conversion (Table 2, entry 1-
7). The complete conversion may be due to the presence of
highly electronegative hetero-atom attached with epoxide groups
which will efficiently promote the ring-opening of the epoxide,
using its –I effect. For styrene oxide, the –I effect of phenyl
group helps to stabilize the electron rich intermediates. Due to
the bulkiness of the attached t-butyl group, t-butyl glycidyl ether
Fig. 1: Comparison of 13C CP-MAS (top) and 13C NMR (bottom) spectra
of CYA-ANIS and monomer, respectively.
To achieve the catalytic CO2 conversion, epichlorohydrin was
chosen as the model substrate. It was observed that in the
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which is an oxygen containing epoxide displayed only 76%
conversion. (Table 2, entry 10). Compared to the hetero-atom
containing epoxides, 1,2-epoxy do-decane and 1,2-epoxy-9-
decene displayed lesser conversion because of the presence of
relatively less polar carbon chain in the side functional group
(Table 2, entry 8-9). This may be the mainreason for the less
reactivity of hetero-atom free carbon chain containing epoxides.
For example, 1,2-epoxy butane showed relatively less
conversion (40%) due to the lesser reaction temperature (65°C).
The reason for choosing lower temperature was its low boiling
point (63°C, Table 2, entry 11). However, this catalyst
combination resulted in better conversion for di-epoxides to their
corresponding di-cyclic carbonates which are highly potential
synthons for the preparation of poly-urethanes via a non-
isocyanate route.16 The interesting point of this strategy is that
the di-cyclic carbonates are less toxic as well as less moisture
sensitive than isocyanetes which is traditionally used for poly-
urethane preparation. In fact, the di-glycydyl ethers displayed
Conditions: substrate, 15 mmol, TBAI 1.67 mol%, temp. 105°C, time 20 h,
CO2gas was taken inside a balloon with 99.5% purity and pressure was
1.02 atm, Product conversion was measured by 1H NMR (Fig. ESI 6 to
ESI 20).For entry 11, temp.was 65°C.
Based on the literature survey and understanding throughout the
work, the following reaction mechanism has been proposed (see
Fig. 2). The first step of this reaction is the epoxide activation
which isachieved by hydrogen bonding between the “N-H” of the
catalyst and “O” atom of the epoxide moiety.17(a) This is
supported by the FT-IR analysis of CYA-ANIS, 1,2-epoxy
hexane and CYA-ANIS-1,2-epoxy hexane mixture (Fig. ESI 21).
The reason behind selecting 1,2-epoxyhexane is its relatively
non-polar carbon chain compared to epichlorohydrin and
relatively higher boiling point (B.P. 118°C, similar like
epichlorohydrin). The study suggested the change in hydrogen
bonding pattern of CYA-ANIS upon addition of epoxide (2500-
3700 cm-1) and no change in FT-IR spectra were observed up to
15 minutes. This suggests the strong hydrogen bonding
between the epoxide oxygen and H-atom from the N-H of the
catalyst (Fig. ESI 22). Moreover, the HOMO-LUMO interaction
between the epoxide and triazine, respectively may enhance the
epoxide activation which increases the positive charge density
on the attached carbon atoms.17(b) Subsequently, the iodide
anion in the reaction mixture opens-up the epoxide by
nucleophilic attack to form the halo-alkoxide anion which can
undergo reaction with CO2 molecule to produce the iodine
substituted-carbonic acid derivatives. This step is the CO2
incorporation step in the organic molecule. Finally, this molecule
undergoes intramolecular SN2 reaction to produce the cyclic
carbonate molecules. The iodide anion is regenerated
andparticipatesagain in thereaction cycle.
better conversion (77%
- 57%) due to the presence of
electronegative oxygen atom attached with the epoxides (Table
2, entry 12-14). However, 1,2,7,8-di-epoxyoctane showed about
57% conversion and the probable reason for this reactivity is
similar to that of carbon chain containing epoxides like 1,2-epoxy
do-decane (Table 2, entry 15).
Table 2: Substrate scope for epoxide to cyclic carbonate
conversion using CYA-ANIS as catalyst.
Fig. 2: Proposed reaction mechanism for epoxide to cyclic carbonate
conversion.
To establish the heterogeneous nature of the catalyst the
recyclability experiment was performed (Fig. 3 and ESI 23). For
this experiment, epichlorohydrin was selected as the model
substrate. After the first cycle, the reaction mixture was diluted
with ethyl acetate and washed three times by centrifugation. The
obtained precipitate was dried and used with fresh TBAI and
epichlorohydrin in the consecutive catalytic cycle. It was
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observed that the catalytic reactivity was retained up to the
fourth cycle where complete conversion of epichlorohydrin was
achieved followed by slight decrease in the conversion to 95%.
After the fifth cycle, the catalyst was washed and collected.
Subsequently, it was characterized using PXRD, TGA, TEM and
FESEM. The results indicate that the nature of the sample was
retained i.e. the amorphousness through PXRD analysis [Fig.
ESI 24(a)]. TGA analysis revealed that the polymer decomposed
gradually from 200-600°C [Fig. ESI 24(b)]. In addition, the
surface morphology of the catalyst was slightly changed due to
the change in the agglomeration pattern, observed in FESEM
analysis [Fig. ESI 24(c)]. Probably, the change in interaction
between the 2D sheets during the reaction resulted into a
Materials: O-diannisidine was purchased from TCI India. Anhydrous
DMF was purchased from spectrochem. Cyanuric chloride and all
epoxides used here were purchased from Sigma Aldrich. Chloroform-d
was purchased from Sigma Aldrich and chloroform was used as internal
standard. DMSO-d6 was purchased from CIL. All chemicals were used as
received.
Preparation of the polymer: 1.84 g (10 mmol) of cyanuric chloride and
3.7 g (15 mmol) of di-annisidine were taken in a 250 ml round bottom
flask. To this mixture anhydrous DMF was added and the reaction
mixture was heated at 130°C for 24 h under nitrogen environment. After
the completion of the reaction, the precipitates were separated by
centrifugation and washed with fresh DMF, followed by methanol and
finally with acetone. Sample was dried inside a 60°C hot air oven for
overnight and utilized further. The schematic of the synthesis protocol is
given in Fig. 1.
different
agglomeration
pattern.
However,
the
TEM
measurement showed that the 2D sheets were retained after the
fifth cycle [Fig. ESI 24(d)]. Interestingly, we have performed the
recyclability experiment in the absence of co-catalyst to support
the heterogeneous nature of the catalyst. The results indicate
that the catalyst was capable to retain its initial activity up to third
cycle and subsequently gradual reduction in the reactivity is
noted (Fig. ESI 25). This may be due to the gradual loss of
catalyst during the recyclability study.
Preparation of monomer: 0.922 g (5 mmol) of cyanuric chloride and 1.7
ml (16 mmol) of annisidine were taken in a 250 ml round bottom flask. To
this 100 ml anhydrous DMF was added and the reaction mixture was
heated at 130°C for 24
h under nitrogen environment. After the
completion of reaction, distilled water as added to precipitate the product
and separate DMF in the water medium. Subsequently, the product was
washed repeatedly (3 times) with water to ensure the complete removal
of starting materials. Finally, the product was dried inside a desiccator
connected to vacuum pump and utilized further (Scheme 2).
Scheme.2: Synthesis protocol for the preparation of monomer of CYA-
ANIS.
Fig. 3: Recyclability experiment using CYA-ANIS polymer catalysis.
Condition: substrate, epichlorohydrin 15 mmol, CO2 fill balloon (1.02 atm,
99.5% pure), time 20 h and temp. 105°C. For each catalytic cycle 93 mg
Catalysis protocol: 15 mmol of epoxide, 100 mg catalyst (CYA-ANIS
polymer) and 93 mg or 1.67 mol% TBAI, were taken in 50 ml Schlenck
round bottom flask with a small magnetic stirrer. One blank glass tube
was kept as condenser above the round bottom flask. On the top of the
glass tube, the balloon attached to the glass stopcock was fitted. All
glass joints were sealed with both grease and teflon tape to minimize the
gas leakage. Subsequently, the set up was vacuumed and backfilled with
99.5% CO2 gas thrice to replace the air from the setup and subsequently
the mixture was heated for 20 h under CO2 environment. After the
completion of the reaction, a small amount of the aliquot was collected in
CDCl3 and the solution was utilized for 1H NMR measurement.
1
(1.67 mol%) TBAI was added, Conversion was measured using H NMR
spectroscopy.
In conclusion, we have developed an efficient triazine containing
polymeric catalyst for epoxide to cyclic carbonate conversion
under ambient CO2 pressure (1.02 atm) in presence of
tertrabultylammonium iodide as co-catalyst. This catalyst mixture
was found to be efficient for the conversion of a wide range of
functionalized mono and di-epoxides into their corresponding
cyclic carbonates under CO2 filled balloon condition. Additionally,
this polymeric heterogeneous catalyst was capable to retain its
activity up to five cycles.
Recyclability Test: Recyclability was performed using epichlorohydrin
as model substrate. After the first cycle, diethyl ether and ethyl acetate
1:1 mixture (~30 ml) was added to the reaction mixture for the catalyst
precipitation and centrifuged at 7500 rpm for 5 minutes to separate all the
insoluble materials. The resulting residue was dried inside the 65°C oven
for 16 h and used for the next cycle. For every cycle, 15 mmol of epoxide
Experimental Section
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CO2 environment in presence of TBAI as co-catalyst (i.e. under balloon
condition). To check the conversion, a small amount of aliquot was taken
in CDCl3 for 1H NMR analysis. The recyclability experiment was carried
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5 cycles (Fig. 3). Furthermore, we performed another
recyclability experiment similar to the previous one but in absence of any
co-catalyst for 4 cycles (Fig. ESI 25).
Acknowledgements
The authors thank DST and IISER Kolkata for funding and
instrumentation facilities, respectively. We thank Miss. Ranita
Samanta for her suggetion during the discussion about the
mechanism for the reactions.
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Keywords:Triazinepolymer•Heterogeneouscatalyst•epoxides,
cyclic carbonates•CO2 fixation• metal free catalyst
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10.1002/asia.201901277
Chemistry - An Asian Journal
COMMUNICATION
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COMMUNICATION
Cyanuric chloride and o-
dianisidine based polymer
(CYA-ANIS) with TBAI was
proven to be an efficient
heterogeneous catalyst for
epoxide to cyclic carbonate
conversion under CO2 filled
balloon (1.02 atm pressure)
condition.
Tanmoy
Biswas,aArjunHalder,bKhusbooShivdasPaliwal,a
Antarip Mitra,aGouriTudu,a Rahul Banerjee,a,b
and Venkataramanan Mahalingam*[a]
Page No. – Page No.
Title
For internal use, please do not delete. Submitted_Manuscript
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