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Review

Direct CO2 Transformation to Aliphatic Polycarbonates

Masazumi Tamura,*[a] Yoshinao Nakagawa,[b] and Keiichi Tomishige*[b, c]
doi.org/10.1002/ajoc.202200445

Asian J. Org. Chem. 2022, 11, e202200445 (1 of 20)


Abstract: Reduction of CO2 emission is an important issue all
over the world, and the development of effective trans-
formation methods of CO2 into valuable chemicals is highly
desirable. Among various potential products derived from
CO2, polymers are one of the promising target chemicals in
terms of the production amount and CO2 fixation to solid
materials. Therefore, the direct synthesis of polycarbonates
from CO2 has recently attracted much attention because
polycarbonates including polycarbonate diols are useful
1. Introduction
CO2 is the main component of greenhouse effect gases, and the
concentration in the atmosphere is increasing year by year due
to our economic growth. Therefore, the temperature steadily
increased by more than 1 K from 1900,[1] which causes various
issues such as abnormal weather, desertification, increase in
seawater temperature and sea level, disruption of ecosystem,
food insecurity and so on. Therefore, the reduction of CO2
emission is the top priority, and the development of effective
methods for CO2 capture and storage (CCS) and/or CO2 capture
and utilization (CCU) is highly required.[2] Transformation of CO2
into valuable chemicals is ideal from the viewpoint of a circular
economy but is difficult due to the high stability of CO2.
Therefore, the development of effective catalysts for the
activation of CO2 and reactants is essential. Recently, many
effective catalyst systems have been developed for the trans-
formation of CO2 and can be divided mainly into two
categories,[3] reductive transformation and non-reduction one.
The reductive one of CO2 can provide HCOOH, HCHO, CH3OH,
CH4, alcohols, alkanes and so on,[4] which need high energy
and/or reducing agents such as H2, hydrosilanes and so on, that
are now primarily made from petroleum. On the other hand,
the non-reductive transformation can provide carbonate deriv-
atives such as organic carbonates, carbamates and ureas, and
these polymers.[5] In the non-reductive one, the oxidation state
of the carbon (+ 4) in CO2 is not changed by the transformation,
and these transformations can be carried out by comparatively
low energy input. Among these chemicals by the non-reductive
one of CO2, the polymers such as polycarbonates, polyur-
[a] M. Tamura
Department of Chemistry and Bioengineering,
School of Engineering,
Osaka Metropolitan University, 3-3-138, Sugimoto,
Sumiyoshi-ku, Osaka 558-8585 (Japan)
E-mail: mtamura@omu.ac.jp
[b] Y. Nakagawa, K. Tomishige
Department of Applied Chemistry,
School of Engineering, Tohoku University, 6-6-07,
Aoba, Aramaki, Aoba-ku, Sendai 980-8579 (Japan)
[c] K. Tomishige
Advanced Institute for Materials Research (WPI-AIMR),
Tohoku University, Katahira 2-1-1, Aoba-ku, Sendai,
980-8577 (Japan)
E-mail: tomi@erec.che.tohoku.ac.jp
This manuscript is part of a special collection on Carbon Dioxide Utilization
in Organic Chemistry.
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Review
engineering plastics and intermediates for polyurethanes.
There are many reports on the synthesis of polycarbonates
from CO2 and cyclic ethers such as epoxides and oxetanes,
however, the reports on the synthesis from CO2 and diols are
limited. In this review, we summarize the recent progress of
direct polycarbonate synthesis from CO2 and diols and
explain the potential and issues for industrialization based on
the characteristics of the reaction systems.
ethanes and polyureas are promising targets because these
polymers are useful engineering plastics and long-term fixation
as solid plastic materials is expected. Polycarbonates are
thermoplastic resins and are mainly divided into aromatic and
aliphatic ones. Aromatic polycarbonates are the most prevailing
ones having bisphenol A derivatives as the main frameworks.[6]
On the other hand, aliphatic polycarbonates are biodegradable
polymers and have recently attracted much attention due to
their high biodegradability, biocompatibility and low toxicity.[7]
Moreover, aliphatic polycarbonate diols are used as intermedi-
ates for the synthesis of polyurethanes.[8]
Polycarbonates are currently produced by the phosgene
method using phosgene as a carbonyl source or transesterifica-
tion of diols and organic carbonates derived from CO or
phosgene as a carbonyl source.[9] Therefore, the direct synthesis
of polycarbonates from CO2 as a carbonyl source is a promising
method substitute for these processes. The most studied
method is the direct polymerization of CO2 and cyclic ethers
such as epoxides and oxetanes. Many effective catalyst systems,
particularly complex catalysts, have been developed, and there
are many excellent reviews on the process.[10] However, this
method has some drawbacks such as handling the unstable
cyclic ethers and narrow scopes due to the limited structure of
the cyclic ethers (only C2 and C3 ethers). Another method for
the synthesis of polycarbonates from CO2 is the direct polymer-
ization of CO2 and diols. The method will be able to supply
various polycarbonates by selecting a variety of diols, which are
safe and easy to handle.
However, the direct polymerization of CO2 and diols is
generally difficult, and the biggest problem is the severe
equilibrium (typically equilibrium yields are below 1%). To
overcome the equilibrium limitation various methods have
been investigated, and the summary of the methods is shown
in Scheme 1. One method is the use of dihalides. This method
produces metal salts,[11–14] which can decrease the energy level
of the product side in the overall reaction because of the
exothermic reaction, leading to overcoming the equilibrium.
Another method is the usage of Ph3P and a strong base of
CyTMG (N-cyclohexyl-N’, N’, N’’, N’’-tetramethylguanidine) as a
water contractor and a trap of halogen,[15] which can overcome
the equilibrium. The use of nitriles such as 2-cyanopyridine and
2-furonitrile[16,17] and gas stripping[18] are also useful for the
removal of water from the reaction system, which overcomes
the equilibrium. Since the reviews on the polymerization of CO2
and diols are very limited,[19] we introduce these methods and
© 2022 Wiley-VCH GmbH

Masazumi Tamura received his B.S. at
School of Science from Kyoto University
with Prof. K. Maruoka in 2003 and M.S.
at Graduate School of Engineering from
The University of Tokyo with Prof. M.
Fujita in 2005. From 2005 to 2012 he
was a researcher working at Kao Corpo-
ration, and during that period he
obtained Ph.D. at Graduate School of
Engineering from Nagoya University
with Prof. A. Satsuma in 2012. Since
2012 he has been an assistant professor
at School of Engineering at Tohoku
University. Since 2020 he has been an
associate professor at Research Center
for Artificial Photosynthesis at Osaka
City University. Since 2022 he is an
associate professor at School of Engi-
neering at Osaka Metropolitan Univer-
sity. His current research interests focus
on the development of heterogeneous
catalysts for organic reactions including
biomass, CO2 and plastics conversions.
Yoshinao Nakagawa obtained his Ph.D.
in 2005 from Graduate School of Engi-
neering, The University of Tokyo under
the guidance of Prof. N. Mizuno. After
4years of postdoctoral research at the
University of Tokyo, he joined the
research group of Keiichi Tomishige at
University of Tsukuba. He moved to
Tohoku University and became an
assistant professor in 2010. Since 2013,
he has been an associate professor. His
current research interests are catalytic
oxidations and reductions of bio-related
chemicals.
Keiichi Tomishige received his B.S., M.S.
and Ph.D. from Graduate School of
Science, Department of Chemistry, The
University of Tokyo with Prof. Y. Iwasa-
wa. During his Ph.D. course in 1994, he
moved to Graduate School of Engineer-
ing, The University of Tokyo as a
research associate and worked with
Prof. K. Fujimoto. In 1998, he became a
lecturer, and then he moved to Institute
of Materials Science, University of Tsu-
kuba as a lecturer in 2001. Since 2004
he has been an associate professor,
Graduate School of Pure and Applied
Sciences, University of Tsukuba. Since
2010, he is a professor, School of
Engineering, Tohoku University. He is
also an adjunct professor, Advanced
Institute for Materials Research, Tohoku
University since 2022. His research inter-
ests are the development of heteroge-
neous catalysts for 1) production of
biomass-derived chemicals, 2) non-re-
ductive conversion of CO2 to useful
chemicals, 3) reforming of biomass tar
and natural gas, and so on.
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Review
compare the methods with the conventional ones in this
review.
2. Polycondensation of CO2, diols and dihalides
with alkaline carbonates into polycarbonates
The first example of the synthesis of polycarbonates derived
from CO2 and diols is the reaction of CO2 and α,ω-dibromo
compounds and diolates of diols, which was reported by Soga
and co-workers in 1977[11] (Scheme 2). In this reaction, potas-
sium diolates were produced in advance from the correspond-
ing diols and potassium, and hence, the method is not a direct
synthesis process of polycarbonates from CO2 and diols. The
reaction requires 18-crown-6-ether as a catalyst for the progress
of the desired reaction. In the absence of the crown ether, the
target polycarbonate was not obtained, and in the absence of
CO2 and crown ether, the corresponding polyethers of the
diolate and dibromo compounds were formed.
High yields were obtained by the reactions conducted at
the optimum conditions such as 353 K, 1–4 L CO2 and more
than 100 mg 18-crown-6. The maximum yield of the polycar-
bonate was 78% in the case of a large amount of CO2 (4 L). In
this case, the ratio of the converted diolate amount to 18-
crown-6 amount is estimated to be 4 (mol/mol), confirming that
18-crown-6 is the catalyst. The scope of the dihalides and
diolates is shown in Table 1. The dichloro compound instead of
the dibromo compound was not effective for the reaction, and
the product yield was low. This result indicates that the
dibromo compounds are suitable for the reaction. Sodium
diolate showed a lower yield than potassium diolate, indicating
that potassium diolate is preferable for the reaction. Dipotas-
sium 4,4’-isopropylidenediphenolate also reacted with CO2 and
the dibromo compound to provide the corresponding polycar-
bonate.
The possible route of the reaction of dipotassium 1,4-
cyclohexanediolate and 1,4-bis(bromomethyl)benzene as a
model reaction was proposed as follows (Scheme 3): At first,
dipotassium 1,4-cyclohexanediolate can easily react with CO2
with/without 18-crown-6 to produce 1,4-cyclohexylene dipotas-
sium dicarbonate, and the reaction is relatively fast. And then,
the produced 1,4-cyclohexylene dipotassium dicarbonate and
4-bromomethylbenzyl bromide react to form the corresponding
polycarbonate in the presence of 18-crown-6 as a catalyst. The
reaction is relatively slow, and the step is the rate-determining
one.
After the finding, Inoue, Oi and co-workers reported the
direct synthesis of polycarbonates from CO2, diols and dihalides
with K2CO3 (Scheme 4).[12] In this reaction, an excess amount of
K2CO3 was necessary (~ 4-fold against that of diol). It is unclear if
K2CO3 is directly used as a carbonyl source or not. However, in
their previous work on the synthesis of asymmetric dialkyl
carbonates from CO2, alcohols and halides, the high yields of
the dialkyl carbonates were obtained by using K3PO4 instead of
K2CO3, while K2CO3 was also an effective base additive.[20]
Therefore, CO2 may not be used as a carbonyl source in the
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Scheme 1. The synthesis of polycarbonates and polycarbonate diols from CO2 and diols (or diolates).

Scheme 2. The formation of polycarbonates from dibromo compounds, potassium diolates and CO2 with 18-crown-6.

Scheme 3. Possible reaction route for the formation of the polycarbonate from CO2, dipotassium 1,4-cyclohexanediolate and 1,4-bis(bromomethyl)benzene.

Scheme 4. The formation of polycarbonates from diols, CO2 and dihalides with K2CO3.

polymerization reaction. Similar reaction systems using strong
bases such as K2CO3 and Cs2CO3 were already reported to be
effective for the synthesis of organic carbonates from CO2,
alcohols and alkyl halides,[21] however, the system was ineffi-
cient for the synthesis of diphenyl carbonate from CO2 and
phenol even by using a large amount of ZnCl2 (about a half
amount of phenol).[22]
Table 2 shows the scope of the diols and dihalides. The
obtained polymers are the alternating copolymer of CO2 with
diols and dihalides. The primary and secondary diols with 1,4-
bis(chloromethyl)benzene as a dihalide provided the corre-
sponding polycarbonates with moderate to high yields, how-
ever, the tertiary diol showed a low yield of the polycarbonate.
When 1,4-dibromobutane and 1,4-diiodobutane reacted with
1,6-hexanediol, the corresponding aliphatic polycarbonates

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Table 1. Scope of substrates in the reaction of dihalo compounds, diolates and CO2 with 18-crown-6 as a catalyst.
Dihalo Diolate/mg 18-Crown- Polycarbonate Yield/ Halogen m.p./K Viscosity
compounds/ 6/mg mg content/%
mg

353–
100 413 2.24 (Br) 0.13
376

500 365

100 50 8.79 (Cl) – –

430 400

127–
200 62 12.53 (Br) 0.06
146

500 345

175–
100 292 8.55 (Br) 0.11
198

500 406

175–
250 330 2.69 (Br) –
192

500

Reaction conditions: dihalo compound, diolate, CO2 2 L, 18-crown-6, dioxane 6 ml, 353 K, 48 h. Reproduced with permission from Ref. [11b]. Copyright 1978
WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

were obtained in low yields (26 and 36%, respectively). It seems
that phenols were not suitable substrates and phenyl ether was
formed from dihalides and phenols. The method gave a higher
yield of the polycarbonate from 1,4-bis(chloromethyl)benzene
and 1,4-cyclohexanediol than the above one using 1,4-
bis(bromomethyl)benzene and diolates despite that the di-
chloro compound was used at the same reaction temperature
(353 K) and reaction time (48 h).
The reaction route was proposed in the following
(Scheme 5). At first, diol and CO2 react to form carbonic acid
monoester in equilibrium, which is transformed to potassium
carbonic acid in the presence of K2CO3. The potassium carbonic
acid reacts with dihalides to afford the corresponding carbo-
nates. The reaction sequentially proceeds to provide the
corresponding polycarbonates. The key to the reaction is the
usage of the moderate basicity of K2CO3, which can form the
potassium carbonic acid and cannot form the alkoxide of
alcohols. Therefore, the formation of the ethers by the
alkylation of alcohols with halides is suppressed.
After about 20 years, Y. Gnanou and co-workers also
investigated the same method of polycarbonate synthesis from
diols, CO2 and dihalides with K2CO3. They optimized the reaction
conditions with various metal carbonates in the polycondensa-
tion of 1,4-benzenedimethanol, 1,4-dibromobutane and CO2 as
a model reaction.[13] Among K2CO3, DBU (1,8-diazabicyclo[5.4.0]-
undec-7-ene), Li2CO3 and Cs2CO3 used as base additives, Cs2CO3
was most suitable, showing higher conversion and Mn of the
target polycarbonate. Based on the studies of various reaction

Scheme 5. The formation of polycarbonates from diols, CO2 and dihalides with K2CO3. Reproduced with permission from Ref. [12]. Copyright 1994 WILEY-VCH
Verlag GmbH & Co. KGaA, Weinheim.

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Table 2. Scope of substrates in the reaction of dihalo compounds, diols and CO2 with K2CO3.
Dihalides Diols Polycarbonates Yield/% Mn Mw/Mn

87 7,900 2.12

90 6,400 1.98

62 7,300 1.66

~2 – –

97 15,800 2.36

26 5,600 1.46

36 6,500 1.35

Reaction conditions: diol 10 mmol, dihalide 10 mmol, K2CO3 40 mmol, atmospheric CO2, NMP 20 ml, 353 K, 48 h. Reproduced with permission from Ref. [12].
Copyright 1994 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

factors, they concluded that the optimal reaction conditions are
373 K, 48 h, 1 MPa CO2 and the feeding ratio of diol: dihalide:
Cs2CO3 = 1 : 1.05 : 4. A little larger amount of dihalides than that
of diols enabled higher conversion and molecular weight.
0.1 MPa CO2 is also applicable to the reaction system, however,
the Mn was decreased (8,000 to 2,600), while the conversions
were similar. Similar to the previous case, an excess amount of
Cs2CO3 was also required for the reaction, although CO2 was
necessary for the reaction progress. It should be noted that
under the optimal reaction conditions the produced polycar-
bonates include self-polycondensation of dibromo compounds
in addition to the alternating copolymers of diols and dihalides,
which may be due to the high reaction temperature, use of
dibromo compounds and a little stronger base of Cs2CO3 than
K2CO3.
They investigated the scope of diols and dihalides (Table 3).
1,4-Bis(chloromethyl)benzene and 1,4-dibromobutane reacted
with 1,6-hexanediol to give the corresponding polycarbonates
in high yields (96 and 98%, respectively) with high average
molecular weights. The yields and molecular weights are higher
than those of the previous case (Table 2),[12] although the
reaction temperature is a little higher (373 K vs 353 K) and CO2
pressure is also higher (1 MPa vs 0.1 MPa). These results indicate
that the optimized method is preferable from the industrial
viewpoint. The reaction of 1,4-dibromobutane with 1,4-, 1,3-
and 1,2-benzenedimethanol proceeded to provide the target
polycarbonates with high yields. Moreover, diethylene glycol
and isosorbide were also transformed with 1,4-dibromobutane
to the target polycarbonates in high yields with adequate
molecular weights. Therefore, the method is also applicable to
the reaction of diols with ether bonds and secondary alcohols.
The proposed reaction route for the polycondensation of
diols, halides and CO2 with Cs2CO3 is shown in Scheme 6. The
carbonate bond can be formed by two routes: (i) the
nucleophilic attack of diols to CO2 in the presence of Cs2CO3 to
form the cesium carbonic acid, and then the nucleophilic attack
of the formed carbonic acid anion to dihalides to provide the
corresponding carbonates (first row). (ii) the direct substitution
of dihalides by Cs2CO3 to form the corresponding cesium
carbonic acid, and then the nucleophilic attack of the formed
cesium carbonic acid to dihalides to provide the corresponding
carbonates (second row). Like these reactions, the produced
carbonates can react with CO2 with the aid of Cs2CO3, and such
reactions successively occur to form the polycarbonates (third
and fourth rows).
At about the same time, Du, Artemyeva and co-workers
reported the synthesis of polycarbonates and poly(ether
carbonate)s by a combination system of Cs2CO3 and
dichloromethane,[14a] which is based on the finding of the
synthesis of dialkyl carbonates from CO2 and alcohols using a
combination of Cs2CO3 and dichloromethane by Saito and co-
workers.[23] The reaction system is so similar to the previously

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Table 3. Selected scope of substrates in the reaction of dihalides, diols and CO2 with Cs2CO3.
Dihalo compounds Diol Polycarbonate Yield/% Mn Mw/Mn (n + m)/n

96 43,200 2.31 1.05

98 27,600 1.81 –

97 22,000 3.63 1.2

96 24,400 3.22 1.09

94 11,100 1.90 1.07

95 10,000 2.32 –

92 18,100 2.26

Reaction conditions: diol:dihalide:K2CO3 = 1:1.05:4 (mmol), 1 MPa CO2, NMP 2 ml, 373 K, 48 h. Reproduced with permission from Ref. [13]. Copyright 2016
Royal Society of Chemistry.

Scheme 6. Proposed reaction route for the formation of polycarbonates from diols, CO2 and dihalides with Cs2CO3. Reproduced with permission from Ref. [13].
Copyright 2016 Royal Society of Chemistry.

reported one except for the type of dihalides (previous reports:
alkyl dihalides (C � 2),[12,13] this work: CH2Cl2). The high molar
ratio of Cs2CO3 to 1,4-benzenedimethanol is necessary, and a
lower molar ratio of Cs2CO3 to 1,4-benzenedimethanol than 2
was not effective for the reaction (Conversion: > 99% (molar
ratio 4)! < 25% (molar ratio 2)) with 6.2 equivalent dichloro-
methane.
The scope of the diols is shown in Table 4. Various diols
were converted to the corresponding polycarbonates in moder-
ate yields (30–70%), and the molecular weight (Mn) was also
moderate (1,000–7,000). In the cases of benzylic diols of 1,4-
benzenedimethanol and 1,3-benzenedimethanol, the produced
polymers mainly had carbonate linkages with no methylene
units, namely simple polycarbonates of CO2 and diols. On the

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Table 4. Scope of diols in polycondensation of diols and CO2 with Cs2CO3 and CH2Cl2.
Dihalo compounds Diol Polymers or oligomers Conv./% Yield/% Mn Mw/Mn

CH2Cl2 > 99 64 1,800 1.23

CH2Cl2 > 99 53 5,000 1.84

CH2Cl2 > 99 57 3,400 1.22

CH2Cl2 86 36 6,600 1.41

CH2Cl2 > 99 63 5,100 1.62

CH2Cl2 94 8 780 1.13

Reaction conditions: CH2Cl2 X mmol, diol 1 mmol, Cs2CO3 4 mmol, 1 atm CO2 NMP, 373 K, 12 h. Reproduced with permission from Ref. [14a]. Copyright 2016
American Chemical Society.

other hand, the reaction with aliphatic diols produced polycar-
bonates with methylene units derived from CH2Cl2. In the case
of hydroquinone, the polymer yield was very low, and
carbonate bonds were not formed, although the conversion
was high (94%). The produced polymers are the alternating
polyether from hydroquinone and dichloromethane.
The proposed reaction route of polycondensation of diols
and CO2 with Cs2CO3 and CH2Cl2 is shown in Scheme 7. At first,
the alkoxide of diols is formed from diols and Cs2CO3, and the
reaction of the alkoxide and CO2 produces the cesium
carboxylate. The formed carboxylate reacts with CH2Cl2 to afford
the intermediate carbonate (Y) as shown in Scheme 7. In the
case of benzylic alcohols, the alkoxide mainly attacked the
carbonate carbon to provide the corresponding carbonate
bond. In the case of aliphatic diols, the alkoxide mainly attacked
the α-carbon of the Cl group to give the ether carbonate bond.
The authors explain the reactivity difference by the difference
of pKa (~ 14.0 for benzylic diols, 14.8 ~ 14.9 for aliphatic diols).
The same group studied the effect of the types of dihalides
in the condensation reaction of diols and CO2 with Cs2CO3,
where various types of linkages were formed such as
carbonates and ethers from diols and dihalides and the types of
the linkages depended on the dihalides.[14b] The proposed
formation routes depending on the dihalides are shown in
Scheme 8. The reaction route in the case of dichloromethane is
the same as shown in Scheme 7. As same as the previous case
(Scheme 7), the alkoxide and carbonate can be firstly produced
from diols and CO2 by Cs2CO3, which is the main route in the
presence of excess CO2, and also the alkoxide can react with
dihalides to form the ether (upper two routes). In the case of
diiodomethane, the ether can be easily formed because iodide
is a good leaving group, and the ether bonds will be mainly
formed in the produced polymers (third route). In the case of

Scheme 7. Proposed reaction routes for condensation of diols and CO2 with Cs2CO3 and CH2Cl2. Reproduced with permission from Ref. [14a]. Copyright 2016
American Chemical Society.

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Scheme 8. Proposed reaction routes for condensation of diols and CO2 with Cs2CO3 and CH2X2 (X=Cl, Br, I). Reproduced with permission from Ref. [14b].
Copyright 2019 Elsevier.

dibromomethane, the intermediate (Z), which is the intermedi- ene polymerization was demonstrated[24] (Scheme 9). High
ate Y with Cl replaced by Br in Scheme 7, is produced from the yields of the corresponding polycarbonates were obtained
carbonate and dibromomethane. The intermediate (Z) can (polycarbonates by acyclic diene metathesis: 60–87%,
mainly react with the carbonate at the α-position of Br group in poly(thioether carbonates): 85–98% yields). The synthesis of
Z to give the polymers with methylene units between polycarbonates with two units was also demonstrated with two
carbonate bonds (Second row from the bottom in Scheme 8) diols such as bisphenol A propoxide (adduct of bisphenol A and
because the concentration of the carbonate is higher than that propylene oxide) and hexadecamethylene glycol[25]
of the alkoxide from diols. (Scheme 10).
As examples of the application of the reaction system of
CO2, diols and dihalides as explained above, the stepwise
synthesis of polycarbonates from CO2, diols and allyl bromide
via acyclic diene metathesis and poly(thioether carbonates)
from CO2, diols, allyl bromide and dithiol via metal-free thiol-

Scheme 9. The synthesis of polycarbonate and poly(thioether carbonates) from CO2, diols and allyl halide and/or dithiols. Reproduced with permission from
Ref. [24]. Copyright 2020 Royal Society of Chemistry.

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Scheme 10. Polymerization of CO2, 1,4-bis(chloromethyl)benzene, bisphenol A propoxide and hexadecamethylene glycol with K2CO3. Reproduced with
permission from Ref. [25]. Copyright 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
3. Polymerization of CO2 and diols into
polycarbonates with R3P/CX4/base system
Kadokawa and co-workers reported the direct polycondensation
of CO2 and 1,4-benzenedimethanol with R3P/CX4/base system in
1998[15] (Scheme 11). This finding is shortly after the study on
polycarbonate synthesis from CO2, diols and dihalides with
K2CO3 by Oi, Inoue and co-workers as introduced above.[12]
This method is the first report on the synthesis of
polycarbonates from CO2 and diols and provides polycarbon-
ates without ether bonds derived from halides (Table 5). 1,4-
Benzenedimethanol and 1,3-benzenedimethanol were con-
verted to the corresponding polycarbonates with n-Bu3P/CBr4/
CyTMG system in DMF solvent, although the reactivity of 1,3-
benzenedimethanol seems to be lower than that of 1,4-
benzenedimethanol. However, the polycondensation of CO2
and diethylene glycol did not occur under the same reaction
conditions. The reaction proceeded with Ph3P/CBrCl3/CyTMG
system in CHCl3 solvent. In the case of linear polyethers such as
di-, tri-, poly-ethylene glycols, the polymerization degree
decreased with increasing molecular weights, indicating that
the reactivity of diols decreased with larger molecular weights.
In the case of 1,6-hexanediol, the yield was low (8.8%) due to
the low solubility of the produced polymers, while the
conversion was about 60%.
The proposed reaction mechanism is shown in Scheme 12.
At first, carbonate anion is formed from CO2 and diol by CyTMG,
and trisubstituted phosphine reacts with tetrahalomethane to
provide phosphonium halide. Anion exchange between the
carbonate anion and phosphonium halide occurs to form a
Scheme 11. The polycondensation of CO2 and diols with R3P/CX4/base system. CyTMG: N-cyclohexyl-N’, N’, N’’, N’’-tetramethylguanidine.
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phosphonium intermediate (A) and the (A) is transformed to (B)
in equilibrium. The nucleophilic attack of the OH group in diols
to the intermediate (B) gives the corresponding dimers via
Arbuzov-type reaction, which is proposed to be the rate-
determining step. In this reaction system, the reaction of halides
and alcohols will not take place because of the low reaction
temperature (room temperature).
4. Polymerization of CO2 and diols into
polycarbonates with CeO2 catalyst and nitriles
as dehydrating agents
Catalytic direct polymerization of CO2 and α,ω-diols was firstly
demonstrated by Tomishige, Tamura and co-workers in 2016
with the combination catalyst system of CeO2 and 2-
cyanopyridine.[16] The work is based on the finding in their
studies on the synthesis of organic carbonates (dialkyl carbo-
nates and cyclic carbonates) from CO2 and alcohols with CeO2
catalyst and organic dehydration agents of nitriles.[26] As
discussed in the introduction, the biggest problem of the
reaction is the equilibrium limitation, and the removal of the
produced water is a key for the catalyst system. They found that
the combination catalyst system of CeO2 catalyst and nitriles as
dehydrating agents, particularly 2-cyanopyridine, was effective
for the direct synthesis of dialkyl carbonates from CO2 and
alcohols with high yields (up to 99%) (Scheme 13), where the
produced water was removed by the hydration of 2-cyanopyr-
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Table 5. Scope of diols in polycondensation of diols and CO2 with R3P/CX4/base system.
Diol Polymers or oligomers Time/h Yield/% Mn DP

3 81 1,200 7

3 40 3,800 23

Reaction conditions: diol 1 mmol, CyTMG 2 mmol, tributylphosphine 1.5 mmol, DMF 1 ml, CBr4 2 mmol, CO2 1atm, r.t.

Diol Polymers or oligomers Time /h Yield /% Mn DP

1 59 4700 36

5 48 4900 28

15 8.8 5500 38

Polyethylene glycol (Mn = 400) 15 75 6600 16

Polyethylene glycol (Mn = 1000) 15 72 6300 6

Reaction conditions: diol 1 mmol, CyTMG 2 mmol, Ph3P 1.5 mmol, CHCl3 0.5 ml, CBrCl3 4 mmol, CO2 1 atm, r.t.

Scheme 12. Proposed reaction mechanism of polycarbonate formation from CO2 and diols with Ph3P/CX4/CyTMG system.

idine to picolinamide over CeO2 catalyst, leading to overcoming
of the equilibrium limitation.
The same catalyst system composed of CeO2 and 2-
cyanopyridine was applied to the direct polymerization of CO2
and 1,4-butanediol, and it showed activity for the reaction
(Scheme 14). Other metal oxides showed no activity for the
polymerization, which tendency is similar to the case of dialkyl
carbonates synthesis from CO2 and alcohols.[26d] The produced
polymers are the polycarbonates from CO2 and 1,4-butanediols,
which were checked by MALDI-TOF/MS (Examples for MALDI-
TOF/MS are shown later). Some OH group-capped polymers
were also detected, which will be derived from the reaction
with 2-picolinamide from 2-cyanopyridine hydration. Figure 1
shows the time course of the reaction with CeO2 and 2-

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Scheme 13. The direct synthesis of dialkyl carbonates from CO2 and alcohols
by the combination catalyst system of CeO2 and 2-cyanopyridine.
cyanopyridine. The conversion smoothly increased to > 99%
with high selectivity of 97%, and the yield reached 97% at 8 h.
At the same time, the Mn reached the maximum of 1,070, but
did not increase at a longer reaction time. Low CO2 pressure,
even 0.5 MPa is also applicable to the reaction system, while
the conversion and Mn were a little decreased (90% conversion
and Mn = 630 at 8 h) under the same reaction conditions. A
stoichiometric amount of 2-cyanopyridine is enough for the
reaction, and similar conversion and Mn were obtained (93%
conversion and Mn = 910 at 8 h) under the same reaction
conditions.
The scope of diols with CeO2 and 2-cyanopyridine catalyst
system is shown in Table 6. α,ω-Linear diols showed high
conversions (93– > 99%), providing the corresponding polymers
in high selectivities (97–99%). The polymerization degrees were
between 7 and 9. 1,5-Hexanediol, a diol with primary and
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secondary OH groups, also provided high conversion and high
selectivity to the polymer, however, the polymerization degree
was a little low (3.7). 2,5-Hexanediol, a diol with two secondary
OH groups, and 2,5-dimethyl-2,5-hexanediol, a diol with two
tertiary OH groups, showed low or no conversion, which will be
due to the steric hindrance around the OH group. The tendency
that the reactivities of the secondary and tertiary alcohols are
low is similar to the case in the synthesis of dialkyl carbonates
from CO2 and alcohols[26e] and arylcarbamates from CO2, anilines
and alcohols[27] with CeO2 and 2-cyanopyridine catalyst system.
The reactivity of 1,4-cyclohexanedimethanol and 1,4-benzenedi-
methanol was lower than that of α,ω-linear diols and the
polymerization degree was also low, which was also related to
the steric hindrance of the cyclic structure.
The polymerization degree is limited in the catalyst system
of CeO2 and 2-cyanopyridine, and one possible cause is the end
OH group capping of the produced polymers by 2-cyanopyr-
idine-derived picolinamide. The authors investigated the effect
of nitriles in the polymerization of CO2 and 1,6-hexanediol, and
the results are shown in Table 7. 2-Furonitirle, 2-cyanopyridine
derivatives and cyanopyrazine were effective, and moderate to
high conversions were obtained.[17] However, the Mn of 2-
cyanopyridine derivatives and cyanopyrazine was not higher
than that of 2-cyanopyridine, while 2-furonitrile showed higher
Mn. 2-Pyridinylacetonitrile, 3-cyanopyridine, benzonitrile and
CH3CN were not effective as nitrile additives. Therefore,
heteroaromatic nitriles with a CN group at the second position
are effective nitrile additives for the reaction. The tendency of

Scheme 14. Direct polymerization of CO2 and 1,4-butanediol with the catalyst system of CeO2 and 2-cyanopyridine.

Figure 1. Time-course of polymerization of CO2 and 1,4-butanediol with the catalyst system of CeO2 and 2-cyanopyridine. (A) Conversion and selectivity, (B)
number average molecular weight (Mn) and dispersity (Mw/Mn). White circle: conversion, black circle: selectivity to polycarbonate, diamond: selectivity to
esters, square: Mn, triangle: Mw/Mn. Reaction conditions: CeO2 0.17 g, 1,4-butanediol 10 mmol, 2-cyanopyridine 100 mmol, CO2 5 MPa, 403 K.

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Table 6. Scope of diols in the direct polymerization of diol and CO2.

Sel./%
Diol t /h Conv./% Polymer Ester† Others Mn Mw/Mn PD

CeO2 + 2-cyanopyridine catalyst system

8 > 99 97 3 <1 980 1.38 9.2
24 99 99 1 <1 930 1.34 7.1
24 99 99 1 <1 1080 1.31 7.5
24 99 99 1 <1 1200 1.33 7.0
24 94 97 3 <1 1650 1.26 8.3

24 93 99 1 <1 530 1.10 3.7

24 6 60 2 38 450 1.01 3.1

24 <1 – – – – – –

24 41 98 2 <1 510 1.04 3.0

24 56 82 11 7 590 1.10 3.6

CeO2 + 2-furonitrile catalyst system

24 > 99 99 1 <1 2,300 1.33 20
24 99 > 99 <1 <1 2,600 1.38 18
24 97 99 1 <1 2,600 1.33 13

24 90 > 99 <1 <1 1,700 1.32 10

24 17 97 <1 3 500 1.02 3.4

Reaction conditions: CeO2 0.17 g, diol 10 mmol, 2-cyanopyridine 100 mmol, CO2 5 MPa (at r.t.), 403 K. Reproduced with permission from Ref. [17]. Copyright
2019 American Chemical Society.

the reactivity is similar to the case of dialkyl carbonate synthesis
from CO2 and 2-cyanopyridine with CeO2[26c–e] and hydration of
nitriles with CeO2 catalyst.[28] At longer reaction times than 30 h,
Mn reached a maximum of about 2,800 with the dispersity of
around 1.4.
The Mn of the produced polymers can be controlled by the
amount of 2-furonitrile and 1,6-hexanediol. As for the effect of
the 2-furonitrile amount, more than the stoichiometric amount
of 2-furonitrile was necessary for the reaction. Mn increased
with increasing 2-furonitrile amount and reached 3,500 at the
amount of 50 mmol 2-furonitrile under the reaction conditions
(Reaction conditions: CeO2 0.17 g, 1,6-hexanediol 10 mmol, 2-
furonitrile 5–50 mmol, CO2 5 MPa (at r.t.), 403 K, 24 h). As for the
effect of the 1,6-hexanediol amount, Mn increased with
decreasing the 1,6-hexanediol amount and reached 5,000
(recorded maximum Mn) at the amount of 1.25 mmol 1,6-
hexanediol under similar reaction conditions (CeO2 0.09 g, 1,6-
hexanediol 1.25–25 mmol, 2-furonitrile 25 mmol, CO2 5 MPa (at
r.t.), 403 K, 24 h), which temperature was a little higher than the
previous case with dihalides.
The scope of diols in the catalyst system of CeO2 and 2-
furonitrile is also shown in Table 6. α,ω-Linear diols showed
high conversion and high selectivity, and the Mn was higher
than the case of CeO2 + 2-cyanopyridine catalyst system. 1,4-
Cyclohexanedimethanol also reacted in high conversion and
selectivity, which reactivity is different from the case of CeO2 +
2-cyanopyridine catalyst system. The polymerization degree
reached 10, which was three times higher than that of CeO2 + 2-
cyanopyridine catalyst system. The reactivity of 2,5-hexanediol,
a diol with two secondary OH groups, was low, which tendency
is similar to the case of CeO2 and 2-cyanopyridine catalyst
system. By using CeO2 + 2-furonitrile catalyst system, most of
the selectivities were higher than those in CeO2 + 2-cyanopyr-
idine catalyst system, and the polymerization degree was about
two-three times higher than that with CeO2 + 2-cyanopyridine
catalyst system.
The difference in the performance between nitriles was
further investigated. The authors compared the MALDI-TOF/MS
spectra of the produced polymers with similar Mn with CeO2 +
2-cyanopyridine and CeO2 + 2-furonitrile catalyst systems (Fig-
ure 2). CeO2 + 2-furonitrile catalyst system showed less forma-

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Table 7. The effect of nitriles with CeO2 in the polymerization of CO2 and 1,6-hexanediol.

Entry Nitrile Conv./% Sel./% Mn Mw/Mn PD

Polymer Monoester Others

1 None <1 – – – – – –

2 97 > 99 <1 <1 2300 1.26 16

2-Furonitrile

3 93 99 1 <1 1400 1.24 9.7

2-Cyanopyridine

4 96 99 1 <1 1100 1.25 7.6

Cyanopyrazine

5 50 46 19 35 600 1.05 4.2

2-Pyrimidinecarbonitrile

6 > 99 99 1 <1 1100 1.22 7.6

5-Chloro-2-pyridinecarbonitrile

7 20 82 18 <1 500 1.14 3.5

3-Methyl-2-pyridinecarbonitrile

8 <1 <1 <1 > 99 – – –

2-Pyridinylacetonitrile

9 3 <1 <1 > 99 – – –

3-Cyanopyridine

10 1 <1 <1 > 99 – – –

Benzonitrile
11 CH3CN <1 – – – – – –

Reaction conditions: CeO2 0.09 g, 1,6-hexanediol 5 mmol, nitrile 10 mmol, CO2 5 MPa (at r.t.), 403 K, 24 h. Reproduced with permission from Ref. [17].
Copyright 2019 American Chemical Society.

tion of the end OH capping polymers by 2-furamide, while the
capped polymers increased at a longer reaction time.[17] There-
fore, one of the causes of the high Mn in CeO2 + 2-furonitrile
catalyst system is the lower capping rate of the end OH groups
in the produced polycarbonates. The difference in the capping
is derived from the difference in the reactivity of the OH group
with the produced amides. The difference in the reactivity
between the OH group and amides was confirmed by the
comparison of the reactivity of amides with 1-hexanol as a
model reaction, showing that the reactivity of picolinamide
with 1-hexanol is 2.4-fold higher than that of 2-furamide.
Considering the usage of polycarbonates as a monomer for
polyurethanes, polycarbonate diols, namely polycarbonates
without capping of the end OH groups, are necessary. There-
fore, the method which does not produce the end-capped
polycarbonates is preferable.
Another cause for the difference in the catalytic perform-
ance is proposed to be the difference in the adsorption strength
of the nitriles on CeO2, which is related to the area of the
reaction field. In these catalyst systems, the nitriles are adsorbed
on the surface of CeO2 via both the coordination of the
heteroatoms (N or O) on the Ce atom and the covalent bonding
between the carbon atom of CN groups in nitriles and the
lattice O atom of the surface of CeO2, forming a strong base
catalyst. The adsorption strength of 2-cyanopyridine is esti-
mated by DFT calculations to be much stronger (Eads =
0.56 eV) than that of 2-furonitrile (Eads = 0.13 eV), meaning
that 2-furonitrile comparatively easily desorbed from CeO2 and
the wide reaction field for polycarbonate diols and CO2 is
retained. The higher reactivity of polycarbonate diols in CeO2 +
2-furonitrile catalyst system was confirmed by the higher Mn of
polycarbonates in CeO2 + 2-furonitrile catalyst system than that
in CeO2 + 2-cyanopyridine catalyst system at the same con-
version level.[17]
The reaction mechanism of polymerization of CO2 and 1,4-
butanediol with CeO2 + nitrile catalyst systems is shown in

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Figure 2. MALDI-TOF/MS spectra of the polymers produced by polymerization of CO2 and 1,6-hexanediol with CeO2 and 2-cyanopyridine (A, Mn = 1,200) and
CeO2 and 2-furonitrile (B, Mn = 1,500) catalyst systems. Reproduced with permission from Ref. [17]. Copyright 2019 American Chemical Society.

Scheme 15, which is based on the studies on the synthesis of
dialkyl carbonates from CO2 and diols[26d] and the adsorption
structure of CeO2 and nitriles.[29] The active species of the strong
base site of N in the CN group is formed by the adsorption of
nitriles (2-cyanopyridine and 2-furonitrile) on CeO2. Diols are
dissociatively adsorbed on CeO2 to form alkoxide adspecies and
an OH group and are activated by the strong base site. CO2 is
easily inserted into the alkoxide adspecies to give the carbonate
adspecies. The activated diol by the strong base site attacks the
carbonate adspecies to form the corresponding dimer and H2O.
The produced H2O is consumed by the hydration of the nitriles
to the amides, resulting in overcoming the equilibrium. The
produced dimer also reacts in the same way, finally forming the
polycarbonate.
The effect of the morphologies of CeO2 such as nanorod,
nanocube and CeO2 nanoparticles was investigated by Yu and
co-workers, showing that among these CeO2 samples, the CeO2
nanorod was the most effective for the reaction;[30] The
obtained polymer amount is about three times higher than that
in the case of CeO2 nanoparticles under the reaction conditions
(CeO2 0.17 g, 1,6-hexanediol 20 mmol, 2-cyanopyridine
100 mmol, CO2 455 mmol, 423 K, 8 h). They concluded that the
high activity for CeO2 nanorods was due to the ability of high
CO2 uptake and strong interaction with CeO2. Based on the in-
situ FTIR analyses of the reaction of CO2 and 1,4-butanediol, the
oxygen vacancy of CeO2 is proposed to be involved in the
reaction mechanism. Moreover, the same group simulated the
process of the CeO2 and 2-cyanopyridine catalyst system to
assess the CO2 emission ratio and cost.[31] From the simulation
of the solvent amounts (THF, H2O, methanol) for separation and
heat integration by vapor recompression cycle, the CO2
emission ratio is reduced by 82.0% (from 30.06 to 5.42 kg-CO2/
kg-PBC) when the solvent amount is reduced to 10%, and
another 19.9% reduction in CO2-e (to 4.34 kg-CO2/kg-PBC) by
the heat integration. The manufacturing cost of products is

Scheme 15. Proposed reaction mechanism of polymerization of CO2 and 1,4-butanediol with the catalyst systems of CeO2 and nitriles.

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reduced by ca. 68% by the combination of the above
simulations (from 5.62 to ca. 1.8 USD/kg).
As above, the combination catalyst of CeO2 and nitriles such
as 2-cyanopyridine and 2-furonitrile directly provides polycar-
bonates from CO2 and diols at a comparatively low reaction
temperature of 403 K, however, the nitrile additives, which are
dehydration agents, are essential for the reaction, leading to
the formation of at least stoichiometric amount of the
corresponding amides by the hydration of the nitriles. The
treatment of the formed amides is necessary, and the methods
for the regeneration of the nitriles from the amides are very
important from the industrial, economical and environmental
viewpoints, although the effective heterogeneous catalysts for
the dehydration of amides such as picolinamide (Na2O/SiO2[26c])
and 2-furamide (MoOx/SiO2[32]) to the corresponding nitriles
have been developed. Moreover, the capping of the end OH
groups in the produced polycarbonates is not desirable and
suppresses the elongation of the produced polycarbonate diols.
5. Polymerization of CO2 and diols into
polycarbonates with CeO2 catalyst and CO2
flow reaction system
Direct polymerization from CO2 and diols without using
dehydrating agents was demonstrated by Tomishige, Tamura
and co-workers, and the equilibrium limitation was overcome
by using a CO2 flow reaction system with the CeO2 catalyst.[18]
The image of the reactor, which is composed of a pear-shaped
flask and a condenser, is shown in Figure 3. The water produced
by the reaction is stripped by CO2 flow to the outside of the
reactor, leading to overcoming the severe equilibrium limita-
tion. Moreover, the evaporation of substrate and solvent is
suppressed by the condenser, which enables the selective
removal of water from the reaction mixture. The reaction
smoothly proceeded under the optimal reaction conditions to
Figure 3. CO2 flow semi-batch reactor and time-course of direct polymerization from CO2 and 1,6-hexanediol with CeO2 catalyst and CO2 flow semi-batch
reactor. Reaction conditions: CeO2 0.10 g, 1,6-hexanediol 2.0 g (17 mmol), diphenyl ether 3 g, triglyme 2 g, CO2 flow rate 200 mL min 1, 483 K. Reproduced
with permission from Ref. [18]. Copyright 2021 Royal Society of Chemistry.
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reach 95% conversion at 96 h, and the selectivity of the polymer
is 97% (Figure 3). At the same time, a maximum Mn of 3,500 was
obtained (Mw/Mn = 2.38). The produced polymer was the
polycarbonate diols that contain few ether bonds, and the end
OH groups are in a free form. CeO2 was the only active metal
oxide among various metal oxides tested, and the reusability of
the CeO2 catalyst was confirmed.
The scope of the diols is shown in Table 8. Various aliphatic
α,ω-diols could be transformed into the corresponding polycar-
bonate diols in high selectivity (polymer +dimer, >99%). Mono-
alcohols such as 1-dodecanol, primary alcohol, and 2-octanol,
secondary alcohol, reacted to give the corresponding dialkyl
carbonates in high selectivity (>99%). 1,2-Propanediol, a vicinal
diol, was also transformed into the corresponding cyclic carbonate
in high selectivity (> 99%).
6. Comparison with conventional reaction
systems based on scope, reaction conditions
and atom efficiency
As mentioned above, the phosgene method is mainly used for the
synthesis of polycarbonates. It is generally conducted by the
interfacial polycondensation method using CH2Cl2 and water, and
tertiary amines or quaternary ammonium salts are used as a
catalyst for the reaction.[9] The reaction is typically carried out at
atmospheric pressure and room temperature due to the high
reactivity of phosgene. However, the method has many drawbacks
such as the use of highly toxic phosgene, formation of inorganic
salts, use of a large amount of organic solvent (mainly CH2Cl2) and
so on. As an alternative method without using phosgene, the
transesterification of disubstituted carbonates and diols is also
applied to the synthesis of polycarbonates in industry. Trans-
esterification of dimethyl carbonate (DMC) and diols are com-
monly conducted by two-step synthesis (Scheme 16): The first
step is the transesterification of DMC and diols, and the second
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Table 8. Scope of alcohols in the direct polymerization or carboxylation with CeO2 catalyst and CO2 flow semi-batch reactor.

Diol or mono-alcohol T/K Conv./% Sel./%

Polymer Dimer Others

453 30 27 73 <1
483 85 75 25 <1
473 58 48 52 <1

473 55 29 71 <1

483 53 - > 99 <1

433 8 - > 99 <1
Diol T/K Conv./% Sel./%
Polymer Cyclic carbonate Others
393 13 <1 > 99 <1

Reaction conditions: CeO2 0.1 g, alcohol 17 mmol, triglyme 2 g, diphenyl ether 3 g, CO2 flow rate 200 ml min 1, 48 h. Reproduced with permission from
Ref [18]. Copyright 2021 Royal Society of Chemistry.

Scheme 16. Two-step synthesis of polycarbonates by transesterification of dimethyl carbonate and diols.

step is polycondensation. Typical reaction temperatures for the
transesterification of dimethyl carbonate and aliphatic diols are
363–443 K and those for the polycondensation are 413–483 K.
Various homogeneous organic and inorganic catalysts such as
Zn(OAc)2, NaH, 1,3-diphenoxytetra-n-butyldistannoxane, 1-n-butyl-
3-methylimidazolium-2-carboxylate, 4-dimethylaminopyridine
(DMAP), CH3COONa, CH3ONa,[33] and heterogeneous catalysts such
as TiO2-SiO2, MgAl hydrotalcite, Mg–Fe/Ti layered double hydrox-
ides, KNO3/γ-Al2O3[34] have been developed. As for the trans-
esterification of DPC and bisphenol A used for AsahiKASEI process,
a higher reaction temperature (~ 533 K) seems to be required due
to the high viscosity of bisphenol A-derived polycarbonates. Ring-
opening polymerization of cyclic carbonates is also an effective
method for the synthesis of polycarbonates, and effective
homogeneous and heterogeneous catalysts have been developed
such as Lipase-immobilized on SiO2, H3PW12O40/CeO2, CeO2 and so
on.[35] However, the scope of the substrates is very limited, and the
substrates of cyclic carbonates are generally produced by using
phosgene and CO as carbonyl sources. Although not discussed in
detail in this paper, CO2/epoxide copolymerization is a promising
method for the synthesis of polycarbonates from CO2, and various
effective complex catalysts have been developed.[10] The reaction
conditions are comparatively mild (reaction temperatures below
373 K and CO2 pressures between 0.1–5 MPa), and the activity is
also high. The scope of substrates is limited and the handling of
explosive epoxides will be also problematic.
To compare the reactivity of the reaction systems, we
summarize the typical reaction conditions for the above conven-
tional and new methods in Table 9. It is difficult to compare the
reaction systems precisely because the reaction conditions and
processes are quite different and sometimes complicated. There-
fore, in this manuscript, we focus on the reaction temperature and
pressure, which are the most important factors for the reaction.
The phosgene process is highly reactive compared with other
processes, and it can be carried out at low reaction temperature
(r.t.) and low pressure (atmospheric pressure), which is strongly
dependent on the high reactivity of phosgene. In the processes
without phosgene, the transesterification was conducted at
comparatively high reaction temperatures (up to 483 K for
aliphatic polycarbonates, ~ 533 K for aromatic polycarbonates) and
atmospheric and reduced pressure, and high yields and polymers
with various Mn can be achieved. Ring-opening polymerization of
cyclic carbonates can be conducted at comparatively low reaction
temperature (293–393 K) at atmospheric pressure, and high yield
and high Mn can be obtained. Therefore, the method has a high
potential for industrialization at the present technical level,
although the scope of substrates is very limited. CO2/epoxide
copolymerization is also performed at comparatively low reaction
temperature (295–373 K) at low-high CO2 pressures (0.1–4.8 MPa).
The method was industrialized, although the scope of substrates is
very limited. Direct polymerization of CO2, diols and dihalides by
alkaline carbonates was performed at moderate reaction temper-

Asian J. Org. Chem. 2022, 11, e202200445 (17 of 20) © 2022 Wiley-VCH GmbH
 Table 9. Typical reaction conditions of the reaction systems for polycarbonate synthesis.
Reaction system Carbonyl Substrate (I)/(II) Catalyst (C) and reagent (R) Step P/MPa T/K t/h Yield/% Mn Reactivity
source (II) molar /Reaction ratea
(I) ratio

Phosgene process COCl2 Bisphenol A Excess (C) Tertiary amine, – 0.1 r.t. – High Controllable High
quaternary ammonium salts
Transesterification of DPC Bisphenol A 1.05 (C) Alkaline metal hydroxide 1 0.1-1 433 – 70 ~ 90 Max Moderate
dialkyl carbonates and diols or amines 2 0.067 538 – > 17,000 ~ low
DPC Aliphatic diols 1–1.2 (C) Zn(OAc)2, – 0.1– 473–483 3 Up to 93 Max
Zn4O[CO2-C6H4-CO2]3 0.0002 ~ 160,000
DMC Aliphatic diols 1–10 (C) Base catalyst 1 0.1 N2 363–443 4–7 Up to 93 Max
(CH3COONa, EtONa, etc.) 2 0.05– 413 ~ 483 2–8 ~ 150,000
0.005
Ring-opening polymerization Cyclic carbonates – (C) Lipase, Zn(C6F5)2, CeO2, – 0.1 293–393 24 Up to 99 Max 31 h 1 (CeO2)

Asian J. Org. Chem. 2022, 11, e202200445 (18 of 20)

etc. 48,000 (70% Conv.)b
CO2/epoxide copolymerization CO2 Epoxide Excess (C) Complex catalysts – 0.1–4.8 295–373 – Up to Max 15,000 h 1
> 99 ~ 300,000 (CoX2Y2)c
Direct polymerization of CO2, CO2 Aliphatic diols + diha- Excess (R) K2CO3, Cs2CO3 – 0.1–1 353–373 12– Up to 98 Max 0.02 h 1 (Cs2CO3)
diols and dihalides by alkaline lides 48 43,200 (> 99% Conv.)d
carbonates
Direct polymerization of CO2 CO2 Aliphatic diols Excess (R) CyTMG (N-cyclohexyl-N’, – 0.1 r.t. 3–15 Up to 81 Max 0.14 h 1 (CyTMG)
and diols by R3P/CX4/base N’, N’’, N’’-tetrameth- 6,600 (~ 80% Conv.)e
system ylguanidine)
(R) Ph3P
Direct polymerization of CO2 and CO2 Aliphatic diols Excess (C) CeO2 – 5 403 8–24 Up to 99 Max 57 h 1 (CeO2)
diols by CeO2 catalyst and ni- (R) Nitriles 5,000 (99% Conv.)f
triles
Direct polymerization of CO2 and CO2 Aliphatic diols Excess (C) CeO2 – 0.1 483 96 Up to 93 Max 3.4 h 1 (CeO2)
diols by CeO2 catalyst and CO2 3,500 (~ 80% Conv.)g
flow reaction system

[a] The reaction rate was determined by the following equation; Reaction rate (h 1) = Converted substrate (mmol)/Reaction time (h)/Catalyst amount (mmol).
[b] Taken from the Reference [35a]. The reaction rate (h 1) is estimated by the surface Ce amount.
[c] Taken from the Reference [36].
[d] Table 4.
[e] Table 5.
[f] Table 6, the reaction rate (h 1) is estimated by the surface Ce amount.
[g] Figure 3, the reaction rate (h 1) is estimated by the surface Ce amount.
Review

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atures (353–373 K) and atmospheric CO2 pressure, however, the
reaction rate of Cs2CO3 is much lower (0.02 h 1) than that of other
catalyst systems. Therefore, if effective catalysts are developed, this
method could be effective, although the formation of salts is
inevitable. Direct polymerization of CO2 and diols by R3P/CX4/base
catalyst system may be a very useful method because the reaction
can be conducted at room temperature and atmospheric CO2
pressure. However, the yield seems to be a little lower than that in
the other cases, and the sacrificial reagent of R3P and CyTMG must
be recovered and regenerated. Direct polymerization of CO2 and
diols by CeO2 catalyst and nitriles is conducted at a moderate
temperature of 403 K and a high CO2 pressure of 5 MPa, and high
yield and comparatively high activity were achieved. However, the
dehydrating agents of nitriles should be recovered and regen-
erated, and the produced polycarbonates are capped by the
produced amides derived from nitriles as described above. For
industrialization, the development of active catalysts at low CO2
pressure and the selection of nitriles whose amides are less
reactive for the produced polycarbonates are necessary. Direct
polymerization of CO2 and diols by CeO2 catalyst and flow reaction
system is performed at a comparatively high temperature of 483 K
and atmospheric CO2 pressure. The catalyst system is very simple
without using additives. However, the reactivity is not so high
(3.4 h 1), and therefore, the development of effective catalyst
systems which can be conducted at lower reaction temperatures
(< 473 K) is necessary for industrialization. Moreover, the recovery
and recycling of unreacted CO2 will be essential.
7. Summary and Outlook
Recent progress in the reaction systems for the synthesis of
polycarbonate from CO2 and diols (diolates) was introduced, and
the potential and issues for industrialization were also explained
based on the performance and reaction conditions of conventional
and new reaction systems. Polymerization of CO2 and diols is limited
by the severe equilibrium, and mainly five reaction systems have
been reported as effective methods, (i) polymerization of CO2,
diolates (from diols) and dihalides by 18-crown-6 (ii) direct polymer-
ization of CO2, diols and dihalides by alkaline carbonates, (iii) direct
polymerization of CO2 and diols by R3P/CX4/base system, (iv) direct
polymerization of CO2 and diols by CeO2 catalyst and nitriles, (v)
direct polymerization of CO2 and diols by CeO2 catalyst and CO2
flow reaction system. All reaction systems have some drawbacks,
and there are still many challenges for practical application. If the
produced polymer is soluble in some solvents, heterogeneous
catalysts are superior to homogeneous ones due to the high
stability, reusability and separability from the reaction mixture and
so on, and therefore, the latter two methods which use heteroge-
neous CeO2 will be more preferable in the synthesis of aliphatic
polycarbonates which are soluble in appropriate solvents. In terms
of the catalytic activity, method (iv), direct polymerization of CO2
and diols by CeO2 catalyst and nitriles, has a high potential for
industrialization, although there are many issues to overcome such
as high CO2 pressure, recovery and recycling of nitriles, and capping
of the produced polycarbonates by the amides from nitrile
hydration. Concerning the reaction system of CeO2 and 2-
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Review
cyanopyridine, the applicability to a flow reaction system was
confirmed in the synthesis of dimethyl carbonate from CO2 and
methanol at moderate to high CO2 pressures.[37] Moreover, LCA for
the synthesis of dialkyl carbonates[38] from CO2 and alcohols and
polycarbonate[31] from CO2 and 1,4-butanediol with CeO2 and 2-
cyanopyridine catalyst system was carried out, showing the
possibility that the catalyst system is superior to the conventional
ones based on energy and greenhouse gas emission. On the other
hand, in terms of a simple reaction system, method (v), direct
polymerization of CO2 and diols by CeO2 catalyst and CO2 flow
reaction system, also has a high potential, however, the reaction
rate is low, and the development of effective catalysts and
processes is essential as well as recovery and recycling of unreacted
CO2. Moreover, if aliphatic diols can be obtained from biomass or
biomass-derived chemicals, the produced polycarbonates are ones
derived from only renewable resources (CO2 and biomass) and
these processes become more useful in terms of carbon neutrality.
At present, there is no effective method for the direct synthesis
of aromatic polycarbonates from CO2 and bisphenol-A derivatives
because the formation of carbonate bonds from CO2 and phenol
derivatives is difficult due to severe equilibrium and low reactivity of
phenol derivatives. However, considering the produced amount of
aromatic polycarbonates is much larger than that of aliphatic ones,
the development of effective catalyst systems for the synthesis of
aromatic polycarbonates is highly required in the future. On one
hand, it is difficult to convert a large amount of CO2 by the
production of polycarbonates from CO2. Therefore, it will be
necessary to combine the method for conversion of CO2 to various
useful chemicals including other polymers and chemicals obtained
by the reductive conversion, to reduce CO2 emissions in total.
Further innovation and development of new methods for CO2
transformation will be required in the future.
Acknowledgements
This paper was financially supported by a “NEDO Feasibility Study
Program” commissioned by the New Energy and Industrial Technology
Development Organization (NEDO).
Conflict of Interest
The authors declare no conflict of interest.
Keywords: Carbon dioxide · Polycarbonate · Diol · Cerium
oxide · Heterogeneous catalyst
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Manuscript received: July 28, 2022
Revised manuscript received: September 14, 2022
Accepted manuscript online: September 18, 2022
Version of record online: October 13, 2022
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