Jointly published by React.Kinet.Catal.Lett.

Kluwer Academic Publishers, Dordrecht Vol. 72, No. 2, 219-227

and Akadémiai Kiadó, Budapest (2001)

RKCL3797

SYNTHESIS OF AROMATIC POLYESTERS BEARING PENDANT

CARBOXYL GROUPS BY PHASE TRANSFER CATALYSIS

Dae-Won Park*, Dong-Heon Ha, Joo-Young Park, Jeong-Yeul Moon and

Hwa-Soo Lee
Department of Chemical Engineering, College of Engineering, Pusan National University, Janjun-
Dong, Kumjung-Ku, Pusan, 609-735, South Korea

Received September 29, 2000

Accepted January 19, 2001

Abstract
Aromatic polyester (PEA) and copolyesters having pendant carboxyl groups are
directly synthesized from isophthaloyl chloride, diphenolic acid and diols by
aqueous/organic two-phase interfacial polycondensation, using phase transfer
catalysts. The yield and molecular weight of the polyester were remarkably
affected by the structure of quaternary ammonium salts and crown ether catalysts.
The phase transfer reaction steps are suggested to explain this phenomena. The
properties of copolyesters were dependent on the original structure of diols.

Keywords: Polyester, phase transfer catalyst, copolyester, isophthaloylchloride,

diphenolic acid, quaternary ammonium salt, crown ether

INTRODUCTION

A number of important polyesters have been synthesized using phase

transfer conditions [1-3]. Since interfacial polycondensation of polyesters has
been reported by Schnell and Conix [4,5], much attention has been paid to
reactive aromatic polyesters. The aromatic polyesters having pendant functional
groups are an important class of functional polymers, because they are expected
for applications as polymer catalysts, amphoteric polyelectrolytes, chelating
agents for metal ions, drug delivery systems and biodegradable polymers.
__________________________________________
*To whom correspondence should be addressed:
Tel: (+82) 51-510-2399, Fax: (+82) 51-512-8563,
E-mail: dwpark2@hyowon.cc.pusan.ac.kr.
0133-1736/2001/US$ 12.00.
© Akadémiai Kiadó, Budapest.
All rights reserved.
220 DAE-WON PARK et al.: POLYESTERS

Most aromatic polyesters have been blended with condensation polymers

such as other polyesters, polyimides and polycarbonates [6]. Therefore,
polyesters bearing pendant reactive groups are expected to find wide
applications in polymer blends [7].
Recently, Wang and Nakamura [8,9] reported the synthesis of aromatic
polyesters bearing pendant carboxyl groups. They compared the reactivity of
polymer catalysts containing an amino acid moiety and tetrabutylammonium
bromide catalyst. Molecular weight of the resulting polyester was remarkably
affected by the phase transfer catalyst and reaction medium.
In the present study, we have investigated the synthesis of aromatic
polyesters by the interfacial polycondensation of isophthaloyl chloride (IPC)
and diphenolic acid (DPA). Quaternary ammonium halides and crown ethers
were used as catalysts. The investigation was focused on the role of different
catalysts in aqueous/organic two-phase polycondensation system. Several
different copolyesters were also synthesized by adding other diols such as
bisphenol A, 3-chloro-1,2-propanediol, N-ethyldiethanolamine to the above
reactant mixture.

EXPERIMENTAL

Isophthaloyl chloride, 4,4’-bis(p-hydroxyphenyl)valeic acid (diphenolic

acid), tetraalkyl ammonium salts, crown ethers and other reagents were obtained
from Aldrich Chemical Co. and were used without further purification.
Polycondensation was carried out in an aqueous/organic two-phase system,
using phase transfer catalysts (PTC). 0.01 mol of IPC in 40 mL of
dichloroethane was added to 0.01 mol of DPA in 90 mL of 1 N aqueous NaOH
solution in the presence of 0.1 g of PTC. After that, the mixture was stirred at
300 rpm and the reaction was continued for 1 h at 25oC. The polyester (PEA)
precipitated was filtered, washed by deionized water and then acetone, and
dried for 8 h at 80oC in a vacuum oven.
Copolyesters were obtained by using 0.01 mol of IPA, 5 mmol of DPA and
5 mmol of diols. The diols used are bisphenol-A(BPA), propylchlorohydrin
diphenolate (PCD), 3-chloro-1,2-propanediol (CPD) and N-ethylethanol amine
(EEA). The same procedure used in polyester synthesis was adapted for the
synthesis of copolyester.
The identification of polyester (PEA) and copolyesters was performed by
FT-IR (Mattson Polaris), 1H-NMR and 13C-NMR (Jeol PMX-60 SI, TMS as an
internal standard). The weight average molecular weight (Mw) of the polyester
was measured by a GPC (Waters), and the yield of the polymer was calculated
by measuring its weight.
DAE-WON PARK et al.: POLYESTERS 221

RESULTS AND DISCUSSION

Synthesis of polyester (PEA)

Polycondensation of IPC and DPA was carried by an aqueous phase/organic

phase interfacial method, using phase transfer catalysts as shown in Scheme 1.
The formation of PEA was characterized by an FT-IR and absorption peaks are
as follows: 2970 cm-1 (-CH3), 1740 cm-1 (-COO-), 1700 cm-1 (-COOH), 1580 cm-1
(benzene rings). The 1H-NMR and 13C-NMR analysis also confirmed the
synthesis of the polyester.

O CH3
O
Cl C C Cl + HO C OH
CH2
CH2COOH

IPC DPA

O O CH3
PTC
C C O C O
aq.NaOH/CH2Cl2
CH2
CH2COOH n

PEA

The catalytic activity of quaternary ammonium salts usually depend on the

corresponding catalyst cation and counter anion [10]. In order to understand the
effects of cation structure on the yield and weight-average molecular weight
(Mw) of PEA, quaternary ammonium chloride catalysts of different alkyl cations
(tetrabutyl, tetrahexyl and tetraoctyl) were used in standard experimental
conditions. Table 1 shows the yield and molecular weight of PEA with different
phase transfer catalysts. The order of catalytic activity is determined as
TOAC>THAC>TBAC.
The mechanism for aqueous/organic two-phase condensation polymerization
can be proposed as in Fig.1, where ClR'Cl is bis-electrophilic (isophthaloyl
chloride), HOROH is the bis-nucleophilic (diphenolic acid), -ORO- is the bis-
nucleophilic anion and Q+ is the phase transfer cation. According to the above
mechanism, the bis-nucleophilic anion located in the aqueous phase ion pairs
with two PTC cations (Eq.2) is transferred into the organic phase, where it reacts with
the bis-electrophilic IPC (Eq.3).
222 DAE-WON PARK et al.: POLYESTERS

Fig. 1. Reaction mechanism of polyester synthesis from IPC and DPA using phase
'
transfer catalyst ( HOROH = DPA, ClR Cl= isophthaloyl chloride, QX =
quaternary ammonium salt PTC )

Bulky quaternary salts, having longer distances between cations and anions,
are generally known to exhibit higher catalytic activity in activating anions [10].
This explains why TOAC is more effective in the reaction of ClR'Cl and
QOROQ in organic phase than THAC and TBHC.
Quaternary ammonium salts with different halide anion (chloride, bromide
and iodide) were used to study the effect of the counter anion on the yield and
molecular weight of PEA. The experimental results in Table 1 show that the
molecular weight of PEA increases in the order Cl-<Br-<I-. The solvation of
anion is an important factor for liquid phase reactions. In a protic solvent like
CH2Cl2, stronger solvation may be expected with a hard anion like Cl- than with
DAE-WON PARK et al.: POLYESTERS 223

a soft anion like I-. Therefore, the order of nucleophilicity will increase in the
order Cl-<Br-<I-, which accords with the order of the reactivity of the quaternary
ammonium halides.

Table 1
Yield and molecular weight of polyester (PEA)a

Run No. PTCb Reaction media Yield(%) Mwc

Q-1 TOAC H2O/CH2Cl2 77.0 26100

Q-2 THAC H2O/CH2Cl2 76.9 22300
Q-3 TBAC H2O/CH2Cl2 75.6 20800
Q-4 TBAB H2O/CH2Cl2 75.3 25800
Q-5 TBAI H2O/CH2Cl2 79.2 30600
C-1 15-C-5 H2O/CH2Cl2 15.6 8500
C-2 18-C-6 H2O/CH2Cl2 32.5 12500
C-3 DCH-18-C-6 H2O/CH2Cl2 24.3 8500
C-4 DB-18-C-6 H2O/CH2Cl2 19.3 6700
S-1 TBAC H2O/chloroform 78.9 20000
S-2 TBAC H2O/toluene 40.6 18600
S-3 TBAC H2O/cyclohexane 12.3 9800

a
Reaction was carried out with 0.01 mol of IPC in 40 mL of CH2Cl2 and 0.01 mol of DPA in
90 mL of aqueous 1N NaOH solution using 0.1g of PTC at 25oC for 1 h
b
TOAC = tetraoctyl ammonium chloride, THAC = tetrahexyl ammonium chloride,
TBAC = tetrabutyl ammonium chloride, TBAB = tetrabutyl ammonium bromide,
TBAI = tetrabutyl ammonium iodide, 15-C-5 = 15-crown-5,
18-C-6 = 18-crown-6, DCH-18-C-6 = dicyclohexano-18-crown-6,
DB-18-C-6 = dibenzo-18-crown-6
c
Weight average molecular weight measured by a GPC

Crown ethers are also known as phase transfer catalysts. They easily form
complexes with potassium or sodium metal cations in aqueous phase and then
move to the organic phase to participate in organic phase reactions. In order to
understand the effects of crown ether structure on the synthesis of polyester
(PEA), 15-crown-5, 18-crown-6, dibenzo-18-crown-6 and dicyclohexano-18-
crown-6 were used as PTCs. The role of crown ethers in the synthesis of
polyester is the transfer of O-RO- like Q+X- of eq. (2) in Fig.1. However crown
ethers form complexes with sodium cations, producing Na+O-RO-Na+, and
transfer it into the organic phase.
Table 1 also shows the yield and molecular weight of PEA with crown ether
catalysts. The catalytic activity of the crown ether catalysts are lower than those
of quaternary ammonium halide catalysts. As the carbon numbers of simple
crown ethers increase from 15-crown-5 to 18-crown-6, the yield and Mw of the
224 DAE-WON PARK et al.: POLYESTERS

polyester increases. The binding constant (Ks) of Na+ with crown ethers shown
in eq. (5) increases with the carbon number of crown ether as reported
previously [11].

Crown + Na+  (Crown-Na)+ (5)

The hole size of 15-crown-5 and 18-crown-6 is reported as 1.7-2.2 and 2.6-
3.2 Å, respectively [12]. The solubility of 18-crown-6 in CH2Cl2 is also known
to be higher than that of 15-crown-5 [10]. All these facts support the better
catalytic activity of 18-crown-6 as compared with 15-crown-5.
When three different kinds of 18-C-6 are compared, the order of catalytic
activity of crown ethers increases as: dibenzo-18-crown-6<dicyclohexano-
crown-6<18-crown-6. This order is the same order as for binding constants,
however, the partition constant, KC = [crown ether]org/ [crown ether]aq, is the
highest for dibenzo-18-crown-6 and the lowest for 18-crown-6 [13]. The
changes in catalyst efficiency of crown ethers can be explained in terms of the
metal-ligand complex stability (binding constant) and partition constant [10].
The effect of complex stability is considered to be more dominant in this work.
The same conclusion was previously reported by Stott et al. [13].
When different types of solvents are used for the synthesis of the polyester
(PEA), dichloromethane and chloroform show higher yield and molecular
weight than with non-polar solvents like toluene and cyclohexane. Cyclohexane
showed the lowest yield and less than 3000 of Mw value since the reactant IPC
was poorly soluble in cyclohexane.

Synthesis of copolyesters

Copolyesters were obtained by substituting half of DPA with different diols,

as shown in Scheme 2. FT-IR analysis confirmed the synthesis of the
copolyesters and the band due to anhydride groups did not appear at 1800-
1850 cm-1. Therefore, linear polyesters having pendant carboxyl groups are
successfully prepared by aqueous/organic two-phase polycondensation. Table 2
shows the yield and Mw of different copolyesters obtained from IPC, DPA and
diols. The copolymer PE-BPA showed the highest yield (45.3%) and molecular
weight (Mw=46,000). The diols having aliphatic chains (CPD, EEA) showed
lower reactivity, probably due to their lower electron density, than did aromatic
chains. In case of PCD, however, the yield and Mw is the lowest even though it
contains aromatic chains. It can be considered that the chlorohydrin functional
group in PCD inhibited the approach of monomers.
The glass transition temperatures (Tg) of the copolyesters are also listed in
Table 2. Tg decreased in the order of PE-BPA>PE-PCD>PE-CPD>PE-EEA.
DAE-WON PARK et al.: POLYESTERS 225

The copolyesters from diols of aliphatic chains showed lower Tg values because
of their relatively higher mobility than those of aromatic chains. One can also
see that PE-BPA has higher Tg than PE-PCD since the latter has soft carboxyl
groups. Thermogravimetric analysis showed the same order of thermal stability
of these copolyesters.

O O CH3
Cl C C Cl + HO C OH + HO R1 OH
CH2
CH2COOH
IPC DPA DIOL

O O CH3 O O
PTC
C C O C O C C O R1 O
aq.NaOH/CH2Cl2
CH2
CH2COOH n

PE-DIOL
CH3
R 1: C Bisphenol A (BPA)
CH3

CH3
C Propylchlorohydrin diphenolate (PCD)
CH2
H
H2COOCH2C C CH2
OH Cl

CHCH2 3-Chloro-1,2-propanediol (CPD)

CH2Cl

CH2CH2NCH2CH2 N-Ethyldiethanolamine (EEA)

CH2CH3
226 DAE-WON PARK et al.: POLYESTERS

Table 2
Effect of various monomers on the yield, molecular weight and glass transition
temperature of copolyesters

Molecular weight
Polymera Diol Yield(%) Tg(ƒC)
(Mw)

PE-BPA Bisphenol A(BPA) 45.3 46,000 95.5

PE-CPD 3-Chloro-1,2-propanediol(CDD) 36.5 25,400 58.5

PE-EEA N-ethyldiethanolamine(EEA) 32.1 21,000 55.4

PE-PCD Propylchlorohydrin diphenolate(PCD) 21.6 26,700 78.6

a
Reaction was carried out with 0.01 mol of IPC in 40 mL of CH2Cl2 and 0.01 mol of DPA in
90 mL of aqueous 1N NaOH solution using 0.1 g of TBAC at 25oC for 1 h

CONCLUSION

The polyester (PEA) was successfully synthesized at room temperature by

aqueous/organic interfacial polycondensation of IPC and DPA, using quaternary
ammonium salts and crown ethers as phase transfer catalysts. The yield and
molecular weight of the polyester are affected by the structure of alkyl chain
length and counter anions of quaternary ammonium salts. In the case of crown
ethers, the size of carbon chain and the type of side chain group are important
factors for the catalytic activity. Several copolyesters are also synthesized by
adding diols into the aqueous phase composed of DPA and aqueous NaOH
solution. Their molecular weight and thermal behavior are dependent on the
nature of diols.

Acknowledgement. This work was supported by the KOSEF (97-0502-0501-

3).

REFERENCES
1. P.W. Morgan: Condensation Polymers by Interfacial and Solution Methods. Interscience,
New York 1965.
2. Y. Imai, S. Abe, M. Ueda: J. Polym. Sci. Polym. Chem. Ed., 19, 3285 (1981).
DAE-WON PARK et al.: POLYESTERS 227

3. B. Zhang, R.A. Weiss: J. Polym. Sci. Polym. Chem. Ed., 30, 83 (1992).
4. H. Schnell: Angew. Chem., 68, 633 (1956).
5. A.J. Conix: Ind. Eng. Chem., 51, 147 (1959)
6. N. Ohtani, Y. Inoue, A. Nomoto, S. Ohta: Reactive Polymers, 24, 73 (1994).
7. N. Ohtani, Y. Inoue, A. Kobayashi, T. Sugawara: Biotechnol. Bioeng., 48, 42 (1995).
8. C. Wang, S. Nakamura: J. Polym. Sci. Part A: Poly. Chem., 33, 2157 (1995).
9. S. Nakamura, C. Wang: Phase Transfer Catalysis: Mechanisms and Syntheses, ACS
Symp. Series 659 (1997).
10. C.M. Starks, C.L. Liotla, M. Halpern: Phase Transfer Catalysis. Chapman & Hall, New
York 1994.
11. D.M. Dishong, G.W. Gokel: J. Org. Chem., 47, 148 (1982).
12. H.K. Frensdorff: J. Am. Chem. Soc., 93, 600 (1971).
13. P.E. Stott, J.S. Bradshaw, W.F. Parish: J. Am. Chem. Soc., 102, 4810 (1980).