Synthesis of Polycarbonate from Dimethyl Carbonate and

Bisphenol-A Through a Non-Phosgene Process

OSAMU HABA,1 ISAO ITAKURA,1 MITSURU UEDA,1 SHIGEKI KUZE2

1
Division of Human Sensing and Functional Sensor Engineering, Graduate School of Engineering, Yamagata University,
Yonezawa, Yamagata 992-8510, Japan

2
Polymer Applications Development Laboratory, Idemitsu Petrochemical Co., Ltd., Ichihara, Chiba 299-0193, Japan

Received 21 October 1998; accepted 20 November 1998

ABSTRACT: A novel nonphosgene process for producing bisphenol-A polycarbonate

(PC) was developed through a transesterification between bisphenol-A (BPA) and
dimethyl carbonate (DMC) and a melt-polycondensation of the resulting bisphenol-A
bismethylcarbonate (1). The transesterification was carried out by heating bisphenol A
in dimethylcarbonate in the presence of Lewis acid catalysts, removing the by-produc-
ing methanol using molecular shieves 4A. Among various catalysts, a combination of
(Bu2SnCl)2O and dimethylaminopyridine gave the best results to produce 1 in 22%
yield for 48 h. Using a larger amount of the molecular sieves further improved the yield
to 80% in 120 h. The resulting 1 was heated under reduced pressure in the presence of
titanium catalysts to produce PC in good yields. The resulting PC had high weight
average molecular weight (Mw) of 75,000. © 1999 John Wiley & Sons, Inc. J Polym Sci A:
Polym Chem 37: 2087–2093, 1999
Keywords: Polycarbonate; dimethyl carbonate; transesterification; distannoxane

INTRODUCTION The alternative methods have been developed

Bisphenol-A polycarbonate (PC) is one of the most
widely used engineering thermoplastics because
of its excellent properties such as high-impact
strength, heat resistance, flame retardancy, di-
mensional stability, and high optical transpar-
ency.1 PC is a condensation polymer usually pre-
pared from bisphenol A (BPA) and phosgene in
dichloromethane solution.2 This process has an
environmental problem because phosgene is well
known for its high toxicity and dichloromethane
is suspected to be a carcinogen and a source of
chlorine in producing of dioxin. Thus the process
without using both phosgene and dichlorometh-
ane should be required.3
Correspondence to: O. Haba, Phone: 181 238 26 3091, Fax:
181 238 26 3101. E-mail: haba@dip.yz.yamagata-u.ac.jp
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 37, 2087–2093 (1999)
© 1999 John Wiley & Sons, Inc. CCC 0887-624X/99/132087-07
for synthesis of PC.2 Transesterification of BPA
and diphenyl carbonate (DPC) and ring-opening
polymerization of macrocyclic oligomers4 are
known. Because the transesterification is
achieved through a melt polymerization, the toxic
solvent is not necessary. There is, however, yet no
variable process to produce DPC from phenol
without the use of phosgene. Synthesis of macro-
cyclic oligomer is essentially the same reaction as
the production of PC from bisphenol A and phos-
gene. In this context, the wholly non-phosgene
process to produce PC would be a very desirable
alternative.
Dimethyl carbonate (DMC) is industrially pro-
duced from carbonoxide and methanol by copper
catalysts.5 Some patents have reported the syn-
thesis of PCs through the transesterification us-
ing DMC instead of diphenyl carbonate.6 This
method is, however, not technically feasible for
the preparation of high molecular weight PC. One
2087
2088 HABA ET AL.
Scheme 1.
reason is that the OH terminal groups of PC
oligomers are far less reactive with the methyl-
carbonate terminal group due to the high basicity
of methoxide anion in contrast with phenoxide
anion. The other reason is that dimethyl carbon-
ate evaporates under the vacuum or high temper-
ature condition necessary to remove by-produced
methanol before high molecular weight PC is ob-
tained.
In order to avoid these problems, the self poly-
condensation of bisphenol A bis(methylcarbonate)
(1) has been investigated.7 Shaikh et al. observed
that high molecular weight PC can be obtained
from the self-polycondensation of 1, but that of
bisphenol A mono(methyl carbonate), which in-
cludes OH terminal group, gives low molecular
weight PC.7a 1 is so less volatile that melt poly-
merization of 1 should allow high temperature
and low pressure enough to remove the by-pro-
duced methanol and dimethyl carbonate. If 1 can
be prepared from dimethyl carbonate and BPA
and be polymerized to give PC, this inexpensive
process should have environmental advantage
with no use of phosgene. However, the synthetic
procedure for 1 is difficult because the reaction
was carried out under pressured condition with
continuous introduction of DMC and removal of
both by-producing methanol and excess DMC,7a
or at ambient pressure, the yield of 1 was not
satisfied .7c This should be caused by the thermo-
dynamically unfavorable process because the phe-
nols have smaller pKa’s than methanol.
To overcome these problems, we have carried
out the synthesis of 1 with continuous removal of
the by-produced methanol using molecular
shieves. We have also investigated the condition
of melt polymerization of 1 to produce high mo-
lecular weight PC. Connecting these two pro-
cesses, we have developed the wholly non-phos-
gene process to yield PC (Scheme 1). This paper
reports the results of this study.
EXPERIMENTAL
Measurement
The infrared (IR) spectra were recorded on a
HORIBA FT-210 spectrometer. The nuclear mag-
netic resonant (NMR) spectra were measured in
CDCl3 on a JEOL EX 270 (1H: 270 MHz, 13C: 68.5
MHz) spectrometer. Tetramethylsilane was used
as an internal standard. Molecular weights were
estimated by a gel permeation chromatography
(GPC) using polystyrene as a standard on a
JASCO TRIROTAR-III HPLC equipped with Sho-
dex KF-80M column at 40°C in THF.
Materials
Dimethyl carbonate and methyl chloroformate
were commercially available and used as re-
ceived. Molecular sieves 4A were purchased from
GL Science Co., and heated at 250°C in vacuo for
24 h. THF was distilled from sodium-benzophe-
none ketyl just before use.
 NON-PHOSGEN PROCESS FOR POLYCARBONATE 2089

Bisphenol A bis(methylcarbonate) (1) from
bisphenol A and dimethyl carbonate.
Procedure A
A typical procedure is as follows: In a 100 ml
round bottom flask equipped with a Soxhlet ex-
tractor were placed bisphenol A (2.0 g, 8.8 mmol),
dimethyl carbonate (50 ml, 600 mmol), BuSn2O
(28 mg, 0.10 mmol) and 3-phenoxytoluene (0.39 g,
2.0 mmol, an internal reference for HPLC). Mo-
lecular sieves 4A were placed in a glass filter in
the Soxhlet extractor. The reaction mixture was
refluxed under nitrogen atmosphere for 48;158
h. A conversion of bisphenol A and yield of 1 were
traced by HPLC. See the text for the results.
Bisphenol A bis(methylcarbonate) (1) from
bisphenol A and methyl chloroformate.
Procedure B
A solution of BPA (10 g, 0.044 mol), triethylamine
(24 ml, 0.18 mol) in THF (320 ml) was cooled to
0 –5°C in an ice bath. Methyl chloroformate (14
ml, 0.18 mol) was added dropwise and then the
reaction mixture was stirred for 24 h at room
temperature. The precipitate formed during the
reaction was filtered off and the filtrate was con-
centrated to 50 ml under reduced pressure. The
residue was poured into 500 ml of water and
precipitate was collected by filtration. The ob-
tained pale yellow solid was stirred in 500 ml of
water for 1 h. The solid was collected by filtration
and recrystallized twice from hexane to give
white needles. Yield 7.8 g (0.023 mol, 53%).
sulting white powder was dried in vacuo for 24 h.
Yield 0.70 g (70%). Mn 5 12,000, Mw 5 26,900.
RESULTS AND DISCUSSION
Transesterification between bisphenol A (BPA) and
dimethyl carbonate (DMC).
Transesterification between BPA and DMC is not
thermodynamically favorable because the higher
acidity of phenol (pKa 5 10) rather than that of
methanol (pKa 5 14). Thus removal of the by-
producing methanol from the reaction system
should be required, and molecular sieves 4A are
suitable for this purpose. The transesterification
reaction was carried out by refluxing a mixture of
BPA (8.8 mmol) and excess DMC (50 ml, 600
mmol) in a presence of catalysts (1.0 mol % of
BPA). By-producing methanol was continuously
removed by 7 g of molecular sieves 4A in a Soxhlet
extractor. As the catalyst, we used distanoxane,8
(Bu2SnCl)2O, which was reported as very strong
transesterification catalyst, and Sc(CF3SO3)3,9
which was reported to be an effective Lewis acid
even in aqueous medium, in addition to conven-
tional Lewis acids10 such as Bu2SnO,7c
Bu2Sn(OCH3)2, and Ti(OiPr)4. The reaction was
traced by means of high pressure liquid chroma-

Melt polymerization of 1
A typical procedure is as follows: In a stainless
steel tube equipped with a mechanical stirrer and
a glass side tube connected to vacuum pump and
N2 line through three-way stop cock were placed 1
(1.0 g, 2.9 mmol) and Ti(OiPr)4 (11 mg, 0.038
mmol). The tube was degassed by the vacuum
pump and filled with nitrogen three times and
then heated in an oil bath to 215°C with stirring.
The stirring was continued for 2 h and then vac-
uumed to 1 mmHg and the temperature was
raised to 260°C. The temperature was main-
tained for 5 h and then cooled to room tempera-
ture. The reaction mixture was dissolved in 10 ml Figure 1. Profiles of transesterification reactions be-
of CH2Cl2 and poured into 100 ml of methanol. tween BPA and DMC. Yield of 1 (a) and conversion of
Precipitation collected by filtration was purified BPA (b) and ln[1/(1-c)](c) as a function of the reaction
by reprecipitation with CH2Cl2/methanol. The re- time, where c is conversion of BPA.
2090 HABA ET AL.
tography (HPLC) using 3-phenoxytoluene as an
internal reference. Figure 1(a) and (b) shows the
conversion of BPA and yield of 1 plotted as a
function of time, respectively. Using Ti(OiPr4),
Sc(CF3SO3)3, and DMAP, consumption of BPA
was not observed within 48 h, while the tin cata-
lysts, (Bu2SnCl)2O, Bu2Sn(OCH3)2, and Bu2SnO,
effectively prompted the consumption.
The reaction proceeds through two stages.
First BPA reacts with DMC to give monocar-
bonate 2 (eq. 1), and the following stage pro-
duces the product 1 (eq. 2). The ability of the
catalysts was estimated from the former reac-
tion, i.e., consumption of BPA. This reaction
should be first-order concerning the concentra-
tion of BPA because excess amount of DMC was
used. Thus we plotted ln[1/(1-c)] vs. time and
showed the profile in Figure 1(c), where c is
conversion of BPA. All plots were linear and
thus the first order reaction was confirmed. The
rate constants were calculated from the slope
and listed in Table I. The most efficient catalyst
(Bu2SnCl)2O gave the rate constant of 7.67
3 1026 sec21. The other tin catalysts were com-
parable to (Bu2SnCl)2O, but for titanium and
scandium catalysts the constants were much
smaller.
N,N-Dimethyl-4-aminopyridine (DMAP) is
known as a good transesterification catalysts.11
We next examined DMAP as a catalyst for the
transesterification between BPA and DMC (en-
try 6 in Table I). The reaction was very slow
with the rate constant of 0.458 3 1026 sec,21
and BPA was hardly consumed. An equimolar
mixture of (Bu2SnCl)2O and DMAP were also
examined as the catalyst (entry 7 in Table I).
The addition of DMAP enhanced the reaction
compared to that by (Bu2SnCl)2O alone, and the
best rate constant of 9.58 3 1026 sec21 was
obtained.
To investigate the effect of the catalysts, we
measured infrared spectra of the mixture of DMC
and the catalyst. The samples were made by dis-
solving the catalyst in DMC followed by evapora-
tion of excess DMC and drying in vacuo. The
carbonyl peak position of the resulting materials
were listed in Table II. In the presence of the
Lewis acids, the absorptions were shifted to
shorter wave number from the original position at
1758 cm.21 An apparent relationship was ob-
served between the absorptions and the rate con-
stants, and the catalyst giving faster reaction
shifted the carbonyl peak to the shorter wave
number. This shift should be interpreted as an
ability to coordinate to the carbonyl groups. The
catalyst giving a large shift has a large ability to
coordinate to the carbonyl group. Thus the acti-
vated carbonyl group can be easily attacked by
the hydroxy group of the phenol. On the other
hand, DMAP showed the slight shift and combi-
nation of (Bu2SnCl)2O and DMAP showed no dif-
ference from (Bu2SnCl)2O only. Thus DMAP does
not act to activate the carbonyl group and should
act as activator for phenolic hydroxy groups.
For all the reactions, the yields of 1 and the
conversion of BPA were very low. This could be
caused by a simple equilibrium problem. Thus
we examined the effect of the amount of molec-
ular sieves. We carried out the same experi-
ments using the combined catalyst of
(Bu2SnCl)2O and DMAP with 9 times the
amount of molecular sieves (64 g). The reaction
profile is shown in Figure 2. The conversion and
yield were improved and reached 100 and 80%,
respectively, within 120 h. The rate constant
was calculated to be 13.5 3 10-6 sec.21 This was
1.5 times larger than the result in Figure 1.
Thus the slow reactions and the low yield of 1
should be improved by developing the more ef-
fective process for the removal of methanol.
 NON-PHOSGEN PROCESS FOR POLYCARBONATE 2091

Table I. Transesterification Reaction Between Bisphenol A and Dimethyl

Carbonatea

Conversion Yield of k 3 10 6
Entry Catalyst of BPA,b % 1,b % sec21

1 Bu2SnO 69 13 6.67
2 Bu2Sn(OCH3)2 60 9 4.69
3 (Bu2SnCl)2O 74 18 7.67
4 Ti(OiPr)4 17 0 0.869
5 Sc(CF3SO3)3 17 0 0.794
6 DMAP 9 0 0.458
7 DMAP/(Bu2SnCl)2Oc 80 22 9.58
a
Reactions were carried out by reflux of a solution of BPA and the catalyst in DMC for 48 h.
[BPA]0 5 0.13 mol z L,21 [Catalyst]0 5 13 mmol z L.21
b
Estimated by HPLC using 3-phenoxytoluene as an internal reference.
c
[DMAP]0 5 [(Bu2SnCl)2O]0 5 13 mmol z L.21

Melt polymerization of bisphenol A bis(methyl under reduced pressure while dimethyl carbonate
carbonate) (1) was being distilled out. The resulting glassy solid
was dissolved in chloroform and poured into
Polymerization of 1 has been reported in the ear-
methanol, and the precipitates were collected by
lier patent,7a in which the polycarbonate having
filtration. The results were listed in Table III. The
high molecular weight (Mw 5 32,000) was formed
polymerizations gave low molecular weight prod-
using Bu2SnO as a catalyst at 240°C for 7 h under
ucts as 4,400 ; 6,500 of Mn’s. In their 1H-NMR
reduced pressure (50 mmHg). However, the reac-
spectra, a small singlet was observed at 3.9 ppm.
tion conditions have not been well investigated to
This peak was identical to the peak due to me-
yield further high molecular weight PC. Thus we
thoxy proton in the spectrum of 1. Thus this peak
re-investigated the polymerization of 1 to opti-
mize the reaction conditions.
Melt self-polymerization of 1 was carried out
with usual transesterification catalysts, Bu2SnO,
Bu2Sn(OCH3)2, (Bu2SnCl)2O, and Ti(O-iPr)4. For
this purpose, 1 was prepared from BPA and
methyl chloroformate for convenience. Oligomer
was prepared at 215°C at the first stage, and then
subjected to further polycondensation at 260°C

Table II. IR Absorption of Carbonyl Group of

Dimethyl Carbonate in the Presence of the Ester
Exchange Catalysts and Rate Constants (k) of the
Disappearance of Bisphenol-A

IR, CAO Stretch k 3 10 6

Catalyst cm21 sec21

(Bu2SnCl)2O/DMAP 1643 9.58

(Bu2SnCl)2O 1643 7.67
Bu2SnO 1727 6.67
Bu2Sn(OCH3)2 1735 4.69
Sc(CF3SO3)3 1743 0.869
Figure 2. Conversion of BPA and yield of 1 vs. reac-
Ti(O-iPr)4 1743 0.794
tion time for the reaction of BPA and DMC with
DMAP 1735 0.458
(Bu2SnCl)2O/DMAP catalyst using 64 g of molecular
none 1758 —
sieves.
2092 HABA ET AL.

Table III. Melt Polymerization of Bisphenol A Bis(methyl carbonate) (1) Using Lewis Acids as Catalystsa

[Catalyst]0, Yield, 2OH contentc,

Catalyst mol % % M n b 3 1023 M w b 3 1023 M n /M w b %

Bu2SnO 0.48 72 4.4 8.0 1.8 47.4

Bu2Sn(OCH3)2 0.50 87 5.0 9.9 2.0 50.9
(Bu2SnCl)2O 0.50 70 4.6 7.0 1.5 37.5
Ti(OiPr)4 0.65 58 6.5 15.9 2.4 2.44
a
Polymerizations were carried out at 215°C for 1 h under ambient pressure and then at 260°C for 2 h in vacuo.
b
Determined by GPC with polystyrene standard.
c
Content of hydroxy groups in the all terminal groups, estimated by 1H-NMR spectra.

should be assigned to terminal groups. On the
other hand, small two doublets were also ob-
served at 6.8 and 7.1 ppm besides the aromatic
peaks of PC at 7.1–7.3 ppm. Because these small
peaks agree with that of bisphenol A, they were
assigned to the 2OH terminal group. The OH con-
tent in all terminal groups was also listed in Table
II. Tin catalysts showed large OH contents com-
pared to the titanium catalyst. Although it is not
clear how the OH terminal groups form, transes-
terification between phenol and methylcarbonate is
thermodynamically unfavorable. In addition, the
earlier report showed incorporation of phenolic com-
pounds into 1 caused the lower molecular weight
PC. Therefore the OH terminal should terminate
the polymerization, and thus further investigation
was carried out using titanium catalyst.
Table IV shows the polymerization results using
almost 0.5 mol % of Ti(O-iC3H7) as a catalyst with
varying the polymerization conditions. As described
above, oligomer was prepared at 215°C at the first
stage, and then subjected to further polycondensa-
tion at the temperature listed in the table under
reduced pressure. The oligomeric product was ob-
tained at 260°C for 2 h, but the longer time (5 h)
increased the Mn to 12,000. The higher temperature
of 320°C gave insoluble product, and the soluble
part was low molecular weight material having Mn
of 11,000. On the other hand, gradual raising of the
temperature, i.e., 240, 260, and 320°C for 2, 1, and
2 hours, respectively, gave soluble product. This
material has relatively high molecular weight as
Mn of 20,000.
CONCLUSION
We have successfully developed a wholly non-
phosgene process for producing PC. This process
includes two steps, i.e., a transesterification be-
tween BPA and DMC to produce 1 and a following
melt polymerization of 1. In the former step, a
combined catalyst of (Bu2SnCl)2O and DMAP was
effective to produce 1 in 80% yield within 120 h. A
more effective process to remove the by-producing
methanol will improve such slow reaction. The
melt polycondensation of 1 in vacuo was succes-
sively carried out by gradual raising of the reac-
tion temperature. The final product has a rela-
tively high molecular weight as Mn of 20,000.

Table IV. Melt Polymerization of Bisphenol A Bis(methyl carbonate) (1) with Ti(O-iPr)4a

[Ti(O-iPr)4]0, Temperature, Time Yield,

mol % °C h % M n b 3 1023 M w b 3 1023 M n /M w b

0.65 260 2 58 6.5 15.9 2.4

0.45 260 5 68 12.0 26.9 2.3
0.51 320 2 63c 11.1d 62.2d 5.6d
0.51 240 ; 320e 5 70 19.6 75.1 3.8
a
Polymerizations were carried out at 215°C for 1 h under ambient pressure and then under the noted conditions.
b
Determined by GPC with polystyrene standard.
c
Insoluble product was obtained.
d
Soluble part in THF.
e
The reaction was conducted at 240°C, 260°C and 320°C for 2, 1, and 2 hours, respectively.
 NON-PHOSGEN PROCESS FOR POLYCARBONATE
REFERENCES AND NOTES
1. Freitag, D.; Grico, U.; Muller, P. R.; Nourvertne, W.
in Encyclopedia of Polymer Science and Engineer-
ing, Vol. 11; Mark, H. F. et al., Eds.; John Wiley:
New York, 1987; p. 649.
2. Clagett, D. C.; Shafer, S. J. in Comprehensive Poly-
mer Science, Vol. 5; Allen, G., Bevington, J. C.,
Eds.; Pergamon Press: Oxford, 1989; p. 345.
3. Freitag, D.; Fenglar, G.; Morbitzer, L., Angew
Chem Int Ed Engl 1991, 30, 1958.
4. Brunelle, D. J.; Sannon, T. G. Macromolecules
1991, 24, 3035.
5. Fox, D. W. in Kirk-Othmer Encyclopedia of Chem-
ical Technology, Vol. 18; Eastman, C. I. et al., Eds.;
Wiley: New York, 1982; p. 492.
6. (a) Brunnelle, D. J.; Smith, W.E. DE-A 2950136,
1978; (b) Bolon, D. A.; Hallgren, J. E. US Pat
2093
4,452,968, 1984; (c) Kanno, T.; Yamato, T. Jpn Pat
284,917, 1990. (d) Kiso, Y.; Shimamoto, K. Jpn Pat
02,251,522, 1990.
7. (a) Watanabe, T.; Teino, M.; Fukuoka, N. Jpn Pat
63,205,318, 1988. (b) Shaikh, A. G.; Sivaram, S.;
Puglisi, C.; Samperi, F; Monotando, G. Polym Bull
1994, 32, 427. (c) Shaikh, A. G.; Sivaram, S. Ind
Eng Chem Res 1992, 31, 1167.
8. Otera, J; Yano, A.; Kawabata, A.; Nozaki, H. Tet-
rahedron Lett 1986, 27, 2383.
9. (a) Kobayashi, S.; Ishitani, H. J. Chem Soc Chem
Commun 1995, 1379. (b) Hachiya, I.; Kobayashi, S.
J Org Chem 1993, 58, 6958. (c) Kobayashi, S.; Wak-
abayashi, T.; Nagayama, S.; Oyamada, H. Tetrahe-
dron Lett 1997, 37, 4559.
10. Otera, J. Chem Rev 1993, 93, 1449.
11. Höfle, V. G.; Steglich, W.; Vorbrüggen, H. Angew
Chem 1978, 90, 602.