Catalysis Today 111 (2006) 292–296

www.elsevier.com/locate/cattod

Aliphatic polycarbonate synthesis by copolymerization of

carbon dioxide with epoxides over double metal cyanide
catalysts prepared by using ZnX2 (X = F, Cl, Br, I)
Il Kim *, Min Ju Yi, Kyoung Ju Lee, Dae-Won Park,
Bu Ung Kim, Chang-Sik Ha
Division of Chemical Engineering, Pusan National University, Busan 609-735, Republic of Korea
Received 10 May 2005; accepted 13 October 2005
Available online 15 December 2005

Abstract
As means of the chemical fixation of carbon dioxide and the synthesis polycarbonates, copolymerizations of carbon dioxide with various
epoxides, such as cyclohexene oxide, cyclopentene oxide and propylene oxide were investigated in the presence of double metal cyanide (DMC)
catalysts. The DMC catalysts were prepared by reacting K3Co(CN)6 with ZnX2 (X = F, Cl, Br, I) together with tertiary butyl alcohol and
poly(tetramethylene ether glycol) as complexing reagents and were characterized by various spectroscopic methods. The DMC catalysts showed
high activity for epoxides and CO2 copolymerization to yield aliphatic polycarbonates of narrow polydispersity and moderate molecular weight.
# 2005 Elsevier B.V. All rights reserved.

Keywords: Carbon dioxide; Catalysis; Copolymerizations; Double metal cyanide; Epoxides; Polycarbonates; Ring-opening

1. Introduction molecular weight distribution compared with similar polyols

synthesized using conventional KOH catalysis, resulting in
Chemical fixation of CO2 is a very attractive subject not only high performance polyurethane products [16]. While DMC
from viewpoint of carbon resource utilization, but also from catalysts offer significant advantages for the ring-opening
increasing environmental concerns. As a kind of potential polymerization of epoxides, few reports have been published on
approach, one of the most promising areas of CO2 utilization is the copolymerization of epoxides with CO2 thereby [17].
its application as a direct material for polymer synthesis. The In this study we have prepared a series of DMC catalysts by
past three decades witnessed the great progress in fixation of changing metal salt, ZnX2 (X = F, Cl, Br, I), which is the most
CO2 into polycarbonates since the creative work of Inoue et al. important component of the DMC catalyst, and investigated the
[1,2]. To date, many excellent reviews in different period effect of the change of the metal salt on various epoxides/CO2
contributed by Kuran [3], Super [4,5], Darensbourg [6–10] and copolymerizations. The resultant copolymers are subjected to
1
Kim [11] have made good description of this topic, where the H NMR spectroscopy, infrared spectroscopy and gel permea-
importance of catalyst was never overestimated. tion chromatography analyses.
Double metal cyanide complexes (DMC) are well-known
catalysts for the ring-opening polymerization of epoxides. 2. Experimental
Recent improvements have made DMC catalysts much more
attractive for commercial manufacture of polyoxypropylene 2.1. Materials
polyols [12–15]. The catalysts are highly active and give
polyether polyols that have low unsaturation and narrow All materials, such as potassium hexacyanocobatate(III)
(K3Co(CN)6), zinc fluoride (ZnF2), zinc chloride (ZnCl2), zinc
bromide (ZnBr2), zinc iodide (ZnI2) and tertiary butyl alcohol
* Corresponding author. Tel.: +82 51 510 2399; fax: +82 51 512 8563. (tBuOH) were purchased from Aldrich and used without further
E-mail address: [email protected] (I. Kim). purification. Cyclohexene oxide (CHO, 98%), cyclopentene
0920-5861/$ – see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.cattod.2005.10.039
 I. Kim et al. / Catalysis Today 111 (2006) 292–296 293

oxide (CPO, 98%) and propylene oxide (PO, 99.5%) were all
purchased from Aldrich and refluxed over calcium hydride
(CaH2), it was then distilled and stored over Linde type 4 Å
molecular sieve. Carbon dioxide of 99.99% purity was used
without further purification. Polymerization grade of poly(-
tetramethylene ether glycol) (PTMEG, molecular weight =
1800) was donated by BASF Korea Ltd.

2.2. Preparation of catalysts

A solution of ZnCl2 (220 mmol) in deionized water

(115 mL) and tBuOH (21 g) is taken in the first beaker
(solution 1). A solution of K3Co(CN)6 (3.15 g, 9.5 mmol) in
deionized water (42 mL) is taken in the second beaker (solution
2). The third beaker contains a mixture of deionized water
(1 mL), tBuOH (20 mL) and PTMEG (3.5 g) (solution 3).
Solution 2 is added to solution 1 dropwise for a period of over
60 min at 50 8C with continuous stirring using a mechanical
stirrer. Solution 3 is then added and the mixture is stirred for an Fig. 1. XPS spectra of various DMC catalysts: (a) DMC-Cl, (b) DMC-F, (c)
additional 3 min. The mixture is then centrifuged. The resulting DMC-Br and (d) DMC-I, and XPS spectrum of (e) K3[Co(CN)6]2.
catalyst (DMC-Cl) cake is dried at 60 8C under vacuum
(30 inHg) to a constant weight. The catalysts using ZnF2 a Varian Gemini 2000 and HP5P CDCl3 as a solvent. Mole-
(DMC-F), ZnBr2 (DMC-Br) and ZnI2 (DMC-I) were prepared cular weight distributions (MWD) were measured using a
by similar procedures. Waters 150-C instrument, operated at 35 8C, with a set at 103,
104 and 500 Å columns (dimethylformamide as a solvent).
2.3. Copolymerization of epoxdies and CO2
3. Results and discussion
Copolymerization of epoxides (CHO, CPO and PO) and
CO2 were carried out in a 50 mL stainless steel autoclave 3.1. Catalyst characterization
equipped with a magnetic stirrer. The dried catalyst (20 mg)
was added into the reactor, followed by adding a desired The DMC catalyst prepared by ZnX2, such as ZnF2 (DMC-
amount of the purified epoxides (5 mL) using a syringe. Then F), ZnCl2 (DMC-Cl), ZnBr2 (DMC-Br) and ZnI2 (DMC-I)
the reactor was capped by the reactor head and entire assembly and K3Co(CN)6 in the presence of tBuOH as a complexing
was transferred to a pressure cell. The reactor was purged with agent (CA) is expected to have a general formula [17]:
several times with CO2. The reactor was then pressurized with Zn3Co(CN)6xZnX2yH2OzCA.
CO2 and then heated at a desired temperature with stirring. The qualitative and quantitative surface formulations of the
After a certain period reaction time, unreacted CO2 was DMC catalysts were investigated by XPS. The XPS spectra of
completely released from the reactor to reduce pressure, the DMC catalysts prepared by using various zinc halides, such
terminating the copolymerization. The polymer powder was as ZnF2 (DMC-F), ZnCl2 (DMC-Cl), ZnBr2 (DMC-Br) and
separated by precipitation using excess methanol followed by ZnI2 (DMC-I) are shown in Fig. 1. The formation of zinc
filtration. The product solution was concentrated to proper hexacyanocobaltate(III) led the binding energy (1023.7 eV) of
volume using a rotary evaporator. The polymer precipitate was zinc atom in ZnCl2 to shift towards lower values. The reaction
filtered off, followed by drying at room temperature in a of ZnCl2 with K3[Co(CN)6]2 ([Zn]/[Co] = 5.0) in the presence
vacuum oven. The solvents used were removed from the filtrate of complexing agents led shift of the binding energy of zinc
by distillation. The polymerization yield was determined by atom to 1021.3 eV. Similar shifts were observed for the DMC
gravimetry. catalysts prepared by using ZnBr2 (1023.7–1020.8 eV) and
ZnI2 (1023.7–1021.1 eV) as metal salts. However, no shift was
2.4. Characterization observed for ZnF2 and a clear F 1 s peak was appeared at
684.8 eV, demonstrating zinc hexacyanocobaltate(III) complex
X-ray diffraction (XRD) patterns of the catalysts were is not formed by using ZnF2.
obtained with a RINT2000 wide angle goniometry 185 using Cu Infrared spectra of K3Co(CN)6 and DMC catalysts (Fig. 2)
Ka radiation at 40 kV and 30 mA. X-ray photoelectorn spec- show a shift of the n(CN) band from 2133.4 cm
1 for
troscopy (XPS) analysis of the catalysts was performed on an K3Co(CN)6 to 2195.9 cm
1 for DMC catalysts. The n(CN)
ESCALAB 250 induced electron emission spectrometer with of free CN
is 2080 cm
1 [17–19]. The n(CN) shifts to higher
Al Ka (1486.6 eV, 12 mA, 20 kV) X-ray sources. IR spectra frequencies demonstrate that the CN
ion acts as not only a s-
of the catalysts were obtained in transmission mode using a donor by donating electrons to the cobalt but also an electron
React IR. 1H NMR spectra of the polymers were performed on donor by coordination to zinc metal. In addition, the band of
294 I. Kim et al. / Catalysis Today 111 (2006) 292–296

Scheme 1. Copolymerizations of epoxides and CO2 and the expected structure

of the resulting copolymers.

DMC catalysts is substantially low, even though they are not

completely amorphous. The crystallinity of the heterogeneous
Fig. 2. Infrared spectra of (a) DMC-Cl, (b) DMC-F, (c) DMC-Br and (d)
DMC catalyst may strongly influence the catalytic activity.
DMC-I. Especially, DMC-I showed most high activity but DMC-F
showed lowest activity (vide infra). Again, the X-ray diffraction
pattern of DMC-F catalyst, which resembles that of crystalline
585.1 cm
1 assigned to n(Co–CN) bond for K3Co(CN)6 shifts K3Co(CN)6, demonstrates that the DMC catalyst is hardly
to lower frequency of 472.6 cm
1 for DMC catalysts. These prepared by using ZnF2.
shifts of n(CN) and n(Co–CN) bands demonstrate that the main
composition of the DMC catalyst, Zn3Co(CN)6, was success- 3.2. Copolymerizations of epoxides and CO2
fully formed by using different zinc halide salts except ZnF2.
Alteration of the crystal structure was investigated by X-ray The copolymerizations of epoxides and CO2 using DMC
diffraction patterns (Fig. 3). The X-ray patterns for DMC catalyst have been carried out at 50 and 80 8C with CO2 at
catalysts prepared in the absence of the organic complexing 9.6 bar. The generalized scheme of the copolymerization and
agent resembled that for highly crystalline zinc hexacyanoco- the proposed structure of the resulting copolymers were
baltate hydrate and it was not active for the homo- and summarized in Scheme 1.
copolymerizations of epoxides. The X-ray patterns for DMC If the alternating copolymerization is perfect, only carbonate
catalysts, which were synthesized in the presence of tBuOH and groups (–OC(O)O–) should be generated. However, kinetically
PTMEG, exhibit broad signals at d-spacing of 5.75, 5.07, 3.59, controlled homopolymerization of CHO results in ether linkage
2.54 and 2.28 Å, ascribing to a cubic lattice structure of (–COC–). The polymers were characterized by FT-IR and 1H
Zn3Co(CN)6 [12,17,20]. This means that the crystallinity of the NMR spectroscopies utilizing the previously established
methodology for similar copolymers produced from other zinc
catalyst systems [4,18].
The isolated polycarbonates produced by using CHO, CPO
and PO as a comonomer were analyzed by 1H NMR in CDCl3,
where the relative amount of ether linkages was determined by
integrating the peaks corresponding to methane protons of the
polyether units containing no CO2 chain in its backbone and
polycarbonate unit formed by the addition of CO2 in its
backbone (Table 1).
The IR spectra of the copolymers resulting from the
copolymerization of CO2 with epoxides are shown in Fig. 4.
The existence of peaks around 1750 cm
1 corresponding to
carbonyl group n(C O) and around 1250 cm
1 assigned to
ether group n(C–O) provide an evidence for the presence of
carbonate unit in the resultant copolymers.
Copolymerizations of CHO, CPO and PO with carbon
dioxide were carried out in the presence of various DMC
catalysts prepared by using different ZnX2, and the results are
summarized in Table 2. In CHO/CO2 copolymerizations,
Fig. 3. XRD curves of (a) DMC-Cl, (b) DMC-F, (c) DMC-Br and (d) DMC-I. DMC-I shows the highest activity (535.09 g-polymer/g-
 I. Kim et al. / Catalysis Today 111 (2006) 292–296 295

Table 1
1
H NMR characterization of polycarbonates produced by the copolymerization of CO2 with various epoxide compounds
1
Monomer H NMR (ppm, CDCl3) Carbonate content ( fCO2 )
Polycarbonate Polyether
CHO 4.2–4.6 3.2–3.6 A4.2–4.6/(A4.2–4.6 + A3.2–3.6)
CPO 4.8–5.2 3.6–4.0 A4.8–5.2/(A4.8–5.2 + A3.6–4.0)
PO 4.9–5.1, 4.0–4.4 3.4–3.6 (A4.9–5.1 + A4.0–4.4)/(A4.9–5.1 + A4.0–4.4 + A3.4–3.6)

Table 2
Results of epoxides/CO2 copolymerizations obtained by using DMC catalysts
Epoxides Catalystsa Tp Time (h) TONb TOFb Mwc Mw/Mn c fCO2 d

CHO DMC-Cl 80 4 526.15 131.55 8900 1.7 0.53

DMC-Br 80 4 527.12 131.78 5100 1.2 0.51
DMC-I 80 4 535.09 133.77 4000 1.2 0.23
CPO DMC-Cl 80 12 492.27 41.18 2300 1.6 0.36
DMC-Br 80 12 501.33 41.78 2900 1.0 0.37
DMC-I 80 12 521.67 43.47 2800 1.4 0.33
PO DMC-Cl 50 24 506.80 21.11 4400 3.9 0.22
DMC-Br 50 24 515.21 21.47 2800 1.0 0.36
DMC-I 50 24 520.60 21.69 3300 1.7 0.32
Polymerization conditions: catalyst = 0.02 g, epoxide = 5 mL, PCO2 (25 8C) = 9.6 bar.
a
DMC-F showed negligible activity.
b
TON in g-polymer/g-Zn and TOF in g-polymer/g-Zn h.
c
Data from GPC.
d
[Carbonate]/([carbonate] + [ether]) ratio determined by 1H NMR spectra (see also Table 1).

catalyst) but the lowest CO2 contents ( fCO2 ¼ 0:23). DMC-F homopolymerization to thermodynamically controlled copo-
shows no activity for copolymerization of CO2 and epoxides lymerization. All polymers showed narrow polydispersities
as expected. It is interesting to note that the carbonate con- with moderate molecular weight ranging from 2300 to 8900.
tents are highest ( fCO2 ¼ 0:53 at 80 8C) when CHO is used as Further mechanistic studies on epoxides/CO2 copolymer-
a comonomer; however, PO comonomer shows the lowest izations by using DMC catalysts are ongoing in order to clarify
carbonate content ( fCO2 ¼ 0:22 at 50 8C) using DMC-Cl the effect of zinc salts and metal cyanide salts by changing the
catalsyts. These results indicate that sterically less bulky catalyst formulations in various ways.
epoxide monomers (say PO) prefer kinetically controlled
4. Conclusions

DMC catalysts prepared by reacting ZnX2 (X = F, Cl, Br, I)

with K3Co(CN)6 in the presence of tBuOH and PTMEG as
complexing reagents were efficient for the copolymerization of
various types of epoxide monomers with CO2. The efficiency of
CO2 fixation was changed according to not only the type of
DMC catalysts but also especially the type of epoxide mono-
mers. DMC-I shows the highest activity but the lowest CO2
reactivity. The DMC catalysts showed high activity (TON >
520 g-polymer/g-Zn) and carbonate content ( fCO2 > 0:23) in
the copolymerizations of CHO and CO2 at 80 8C and
PCO2 ¼ 9:6 bar. In the case of PO/CO2 copolymerizations,
polymer yield was high but carbonate content was relatively low
due to kinetically controlled homopolymerization.

Acknowledgements

This work was supported by the Basic Research Program

(grant no. R01-2003-000-10020-0) of the KOSEF, the BK 21
Fig. 4. The IR spectra of aliphatic polycarbonates synthesized by copolymer- Project, the CUPS (ERC) and the NRL for partial financial
izations of carbon dioxide and (a) CHO, (b) CPO and (c) PO. support.
296 I. Kim et al. / Catalysis Today 111 (2006) 292–296

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