Macromol. Chem. Phys.

2002, 203, 2245–2250 2245

Full Paper: To prepare poly(lactic acid) (PLA) with

improved mechanical properties, high-molecular-weight
poly(L-lactic acid) (PLLA) was synthesized by the direct
polycondensation of lactic acid in solution phase. During
polymerization, the molecular weight of PLA was influenced
by the water content present in the solution; thus, the
experimental apparatus was designed to remove the water
efficiently and this study was focused on the optimization of
the polymerization conditions such as polymerization time,
solvent, and kinds of catalyst, etc. Additionally, to search for
a good catalyst in the polymerization, the mixed oxide
catalysts were synthesized by sol–gel method and it was
characterized by XRD and BET. The results show that the Mv
of PLA obtained was about 33 000, when 0.2 wt.-% of
SnCl2
2H2O was used as a catalyst in the polymerization.
The DSC study shows that the thermal properties of PLA such
as Tg and Tm were influenced by the kind of solvent as well as
the molecular weight of PLA.
The effect of various kinds of stannous compounds on the
molecular weight of PLA synthesized in solution polymer-
ization with molecular sieve.

Synthesis of High-Molecular-Weight Poly(L-lactic acid)

by Direct Polycondensation
Ki Woong Kim, Seong Ihl Woo*
Department of Chemical and Biomolecular Engineering & Center for Ultramicrochemical Process Systems(CUPS), Korea
Advanced Institute of Science and Technology(KAIST) 373-1, Guseong-dong, Yuseong-gu, Daejeon, 305-701, Republic of Korea
Fax: 82-42-869-8890; E-mail: siwoo@mail.kaist.ac.kr

Keywords: catalysis; polycondensation; poly(lactic acid); thermal properties

Introduction
Until now, the development of plastics is focused on the
mechanical properties such as mechanical strength, du-
rability, processability, and transparency to replace materi-
als such as wood and metals in many uses, and it has been
paid attention to the new light material since the 1950’s.
However, the non-degradability characteristic of such
plastics raised serious environmental problems such as
the lack of landfill space, the poisoning of soil, and the
poisonous gases generated during the incineration. To
overcome these environmental problems, several types of
biodegradable polymers have been studied such as poly-
[(3-hydroxybutyrate)-co-(3-hydroxyvalerate)] (Biopol;
Zeneca), blends of starch and poly(vinyl alcohol) (Mater-
Bi; Novamont), polycaprolactone (Tone, UCC; Placcel,
Daicel) and poly(butylenesuccinate) (Bionolle; Showa
High Polymer).[1] These polymers are degradable in soil,
water or compost, but they suffer from low transparency and
a poor mold resistance. Among these biodegradable
polymers, poly(lactic acid) (PLA) has been acknowledged
for the use of packaging material and commodity due to its
good transparency, mechanical strength and safety. So far
PLA has been produced by a multi-step process called ring-
opening polymerization, including the production and the
isolation of intermediate lactide.[2–4] During this process,
water is not produced, so high-molecular-weight PLA can
be synthesized. However, as a result of the high process
costs of synthesizing and purifying lactide, PLA use has
beenrestricted to medical applications such as suture ma-
terials. Thus, the proposed work was undertaken to
synthesize high-molecular-weight PLA by direct polycon-
densation to find its better applicability in packaging
material and commodity. However, it was reported that it
was very difficult to obtain high-molecular-weight PLA by
direct polycondensation because of equilibrium between

Macromol. Chem. Phys. 2002, 203, No. 15 ß WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2002 1022-1352/2002/1510–2245$17.50þ.50/0
2246
free acids, water and polyesters causing difficulty in
removing water as a by-product.[5–8] To solve these pro-
blems, the polymerization conditions were optimized by
screening various catalysts such as SnCl2
2H2O, SbCl3,
SnO, tin trifluoromethanesulfonate, LaCl3, TiO2 and TiO2/
SnO2. In this contribution, we will present the influence
of process variables on the molecular weight of PLA
synthesized by direct polycondensation.
Experimental Part
Solution Polymerization
Using a 250-ml reaction vessel equipped with a Dean–Stark
trap, the solution polymerization was carried out by
varying the polymerization temperature, solvent, concen-
tration of monomer, and the amount of catalyst and kinds
of catalyst including stannous compounds, chloride cata-
lysts and mixed-oxide catalysts in N2 atmosphere. An
aqueous solution of L-lactic acid (85%), used as a starting
material, was purchased from Aldrich Co. m-Xylene (99.9%)
was mostly used as solvent. Two different polymerization
methods were carried out during this study. One polymeriza-
tion method was carried out through the azeotropic dehydra-
tion at 138 8C for 48–72 h without using a molecular sieve as a
drying agent. The reaction mixture was concentrated to about
half of the volume, and then the resulting mixture was poured
into methanol. Precipitated polymers were collected by suction
filtration and dried under reduced pressure, and then white
powders of PLA were obtained. The other polymerization
method was carried out using a molecular sieve (3 Å) as a
drying agent to remove small amounts of water dissolved in the
organic solvent. In the first step, the azeotropic dehydration
was carried out for 30 h at 138 8C using a Dean–Stark trap
which removed about 12 ml of water, while m-xylene was used
as a solvent. Thereafter a tube packed with a molecular sieve
(3 Å) was mounted on the reactor in the place of the Dean–
Stark trap so as to recycle the distilled azeotropic mixture
through the molecular sieve. The resultant was polymerized at
138 8C for 30 h. While replacing the Dean–Stark trap with the
tube packed with molecular sieve (3 Å), the vessel was purged
with N2 to maintain the inert atmosphere. When methox-
ybenzene was used as a solvent, the polymerization was carried
out at 154 8C. The reaction was carried out for 30 h at the same
temperature. After the reaction mixture was concentrated to
about half of the volume, the following steps were the same as
for the above-mentioned polymerization method.
Preparation of SnO2 /TiO2 Using the Sol–Gel Method
8.37 g of SnCl2
2H2O was dissolved in 100 ml of ethanol by
heating at 80 8C for 3-h under vigorous stirring and reflux.
Then, the desired amount of Ti(OBu)4 was added to the
SnCl2
2H2O solution, and the reaction was carried out at 80 8C
for 24 h in the closed vessel. The mixture was dried by using the
rotary vacuum evaporator at 70 8C for 7 h and calcined at
500 8C for 5 h (heating rate ¼ 2 K/min). Finally, a white powder
of mixed oxide catalyst was obtained.[9]
K. W. Kim, S. I. Woo
Analysis and Characterization
The 1H NMR spectra for identification of PLA and
measurement of M n of PLA were recorded on a Bruker
AMX-500 FT-NMR apparatus. The sample solution for
the analysis of PLA structure was prepared by dissolving
100 mg of polymer into 1 ml of CDCl3. The molecular
weight of PLA was measured by the intrinsic viscosity
method, while the relative viscosity was determined in
chloroform (0.2 g/dl) at 30 8C by using a viscometer (46460-
50 Tube, Cannon-Fenske). The intrinsic viscosity was
calculated from the equation of Solomon–Ciuta. The Mark–
Houwink equation is as follows.[10]
0:82
½Z ¼ 1:29  104M v ð1Þ
Differential scanning calorimetry (DSC) curves were ob-
tained using a Dupont TA 2010 thermal analyzer equipped with
a 951 DSC cell. Temperature scans were performed at a heating
rate of 10 K/min under nitrogen purge and X-ray diffraction
(XRD) pattern analyses were performed using a Rigaku D-
MAX-RC diffractometer and Cu-Ka radiation (l ¼ 1.5405 Å)
operated at 45 mA and 40 kV. These diffractograms were
recorded in the range of 2y between 108 and 808 with 0.018
resolutions.
Results and Discussion
Solution Polymerization Without
Using a Molecular Sieve
In this polymerization, it is very important to reduce the
water content efficiently as mentioned above. So, the
monomer was distilled by heating at 100 8C for 24 h in N2
flowing to remove water at the early stage in this research.
However, it resulted in the formation of dimer and trimer of
lactic acid or other impurities as well as the removal of
water. Because of the side effects of distillation, the
distillation step had a bad effect on the molecular weight of
PLA and this experimental data was based on the PLA
synthesized without the distillation step.
Figure 1 shows the effect of catalysts on the molecular
weight of PLA. This polymerization was carried out at
138 8C for 48 h, where the concentration of monomer was
50 g/100 ml and the amount of catalyst was 0.1 wt.-%. As
shown in Figure 2, SnCl2
2H2O had a better activity than
any other catalyst, and the molecular weight of PLA was
about 23 000 when SnCl2
2H2O was used as a catalyst.
Here, it is necessary to understand the better activity of
SnCl2
2H2O for polymerization. Although the reaction
mechanism of the dehydrative condensation for the stan-
nous catalysts is not yet understood, a possible mechanism
for the catalytic activity of the stannous compounds may be
shown in Figure 2.[11] As shown in Figure 2, SnCl2
2H2O
undergoes the self-condensation to form an activated
hydrate form 1 and HCl. The terminal carboxyl of the
oligo(L-lactic acid) reacts with hydroxyl of reactant 1 to
produce water and the reaction center 2. The hydroxyl
Synthesis of High-Molecular-Weight Poly(L-lactic acid) by Direct Polycondensation
Figure 1. The effect of catalysts on the molecular weight of PLA in solution.
terminal of oligo(L-lactic acid) should be coordinated
toward the reaction center 3 so that condensation may be
induced around the metal such as tin so as to form polymer
4 having ester-linkage and an activated hydrate form. It can
be thought that the polycondensation proceeds via such a
cycle. Figure 3 shows that the molecular weight of PLA
synthesized was about 30 000 when 0.2 wt.-% of SnCl2

2H2O was used. However, when more than 0.2 wt.-% of
SnCl2
2H2O was used, the rate of reaction and the molec-
ular weight was decreased because a large amount of
catalyst accelerated not only the polycondensation but also
the depolymerization. As shown in Table 1, TiO2/SnO2
catalysts were synthesized with Ti/Sn between 1:1 and
0.4:1 (molar ratio). The Mv of PLA was 6 500–10 000.
Especially, it increased with an increasing ratio of Ti/Sn. To
confirm this result, the crystalline structure of these cata-
lysts was identified by XRD. According to Figure 4, only a
SnO2 crystalline structure appeared in the case of Ti:Sn ¼
0.4:1.[12] As Ti content was increased, the intensity of peak
at 25.18 and 48.88 was increased. It shows that TiO2 with
anatase structure was formed in the SnO2 crystalline
structure (TiO2/SnO2). However, the molecular weight of
PLA synthesized using TiO2/SnO2 catalysts was not high. It
is thought that TiO2/SnO2 catalyst was very hydrophilic and
did not have proper Lewis acid sites (related to positive
charge excess shown by Thomas et al.[13,14]) generated
from a Sn–O–Ti ‘‘hetero-linkage’’ because they were not
2247
mixed homogeneously according to XRD results. For
example, when Ti/Sn ¼ 0.4:1, only a SnO2 crystalline
structure appeared, and the Mv of PLA synthesized in the
solution phase was about 6 500.
Solution Polymerization with Molecular Sieve
Figure 5 shows the effect of various stannous compounds
such as SnCl2
2H2O, SnO, Sn powder and tin trifluoro-
methanesulfonate on the molecular weight of PLA. The
concentration of monomer was 50 g/100 ml and the amount
of catalysts was 0.2 wt.-%. Like the polymerization without
molecular sieve, SnCl2
2H2O had a good activity and the
M v of PLA synthesized was about 33 000. This value is a
little bit higher than that of PLA synthesized in solution
polymerization without using molecular sieve. The remark-
able increase in the molecular weight was not observed
because it is an irreversible process where molecular sieve
will get saturated as polymerization proceeds even though
zeolite is the most effective drying agent to reduce the
dissolved water content in organic solvents. When TiO2/
SnO2 (Ti:Sn ¼ 1) catalysts was used, the Mv of PLA was the
same as that of PLA synthesized in solution polymerization
without using molecular sieve. Figure 6 shows the effect of
solvent on the molecular weight of PLA. According to
Figure 6, the reaction rate in the polymerization using meth-
oxybenzene as a solvent is faster than that in the polymer-
2248 K. W. Kim, S. I. Woo

Table 1. The change of molecular weight of PLA synthesized in

the solution polymerization without using molecular sieve.

Catalyst Ti/Sn Surface Average pore Mv

area diameter

mol:mol m2/g Å

SnO2/TiO2-1 1: 1 74 74.4 10 600

SnO2/TiO2-2 0.8: 1 54 67.8 8 700
SnO2/TiO2-3 0.4: 1 88 61.3 6 500

ization using m-xylene as a solvent at the early stage due to a

higher polymerization temperature (154 8C, the boiling
temperature of methoxybenzene). However, the molecular
weight decreased rapidly in 48 h because of the poor
thermal stability of PLA; PLA belongs to the group of
polymers that are relatively sensitive to thermal degrada-
tion. Several reasons which can be given for its poor
stability are:[15]

(1) Hydrolysis by trace amounts of water, catalyzed by

hydrolyzed monomer.
(2) Zipper-like depolymerization, catalyzed by the re-
maining polymerization catalysts.
(3) Oxidative, random main-chain scission.
(4) Intermolecular transesterification to monomer and
oligomeric esters.
(5) Intramolecular transesterification resulting in forma-
Figure 2. The mechanism of SnCl2
2H2O in the polycondensa-
tion of the monomer and oligomeric lactides of low
tion. L represents ligands such as carboxylate, carboxyl, hydroxyl molecular weight.
etc.
In fact, it was observed that the reaction mixture in the
melt turned black after 48 h when methoxybenzene was

Figure 3. The effect of the amount of SnCl2
2H2O on the

molecular weight of PLA synthesized by in solution polymeriza- Figure 4. The XRD of TiO2/SnO2 catalysts. (a) T/Sn ¼ 0.4:1 (b)
tion without using molecular sieve. Ti/Sn ¼ 0.8:1 (c) Ti/Sn ¼ 1:1 (molar ratio).
Synthesis of High-Molecular-Weight Poly(L-lactic acid) by Direct Polycondensation 2249

Figure 5. The effect of various kinds of stannous compounds on

the molecular weight of PLA synthesized in solution polymeriza-
tion with molecular sieve.

used as a solvent. To investigate the thermal properties of

PLA in the function of solvent, DSC was used. The glass-
transition temperature (Tg) and its location and breadth
supply valuable information about the homogeneity of the
crystalline phase and the degree of interaction between
crystalline and amorphous phase. Figure 7A shows that Tg
and the melting tempoerature (Tm) increased to 59 8C and
159 8C, respectively, with molecular weight of PLA when
m-xylene was used as the solvent. But Figure 7B shows that
the exothermal peak was decreased and Tm decreased to
about 145 8C with the molecular weight of PLA when
methoxybenzene was used as a solvent. Based on the de-
crease of crystalline peak and the decrease of Tg and Tm, it

Figure 7. DSC thermogram of PLA. (A) m-xylene: (a) 24 h

Figure 6. The effect of solvents on the molecular weight of PLA. (b) 36 h (c) 48 h (d) 60 h; (B) methoxybenzene: (a) 24 h (b) 36 h
(a) m-xylene (b) methoxybenzene. (c) 48 h (d) 60 h.
2250
was thought that the crystalline L-form was partially
changed to the amorphous D,L-form by interaction between
the methoxy group in the solvent and reactant or racemiza-
tion during the reaction. Consequently, these side reactions
as well as depolymerization resulting from higher poly-
merization temperature had a bad effect on the molecular
weight of PLA when methoxybenzene was used as the
solvent. To confirm the above thought, the crystalline
structure of PLA was investigated by XRD. According to
Figure 8, four characteristic peaks appeared at 2y ¼ 14.68,
16.688, 19.148, and 22.278. As the polymerization pro-
ceeded, a shift of the peaks did not occur but the intensity of
the peaks at 2y ¼ 14.68 and 16.688 decreased. This shows
that the crystalline perfection was decreased due to
racemization and that the crystalline L-form was partially
changed to the D,L-form.
Conclusion
PLA was synthesized by direct polycondensation using a
reactor equipped with the Dean–Stark trap (water separa-
tor). A molecular sieve was used as a drying agent to reduce
Figure 8. The XRD results of PLA synthesized in the solution
polymerization using methoxy benzene as a solvent (a) 24 h (b) 36 h
(c) 48 h.
K. W. Kim, S. I. Woo
the small amount of water in the organic solvent. The longer
the polymerization time, the higher the molecular weight of
PLA became, because of the high activation energy of the
polycondensation. The highest molecular weight was about
33 000 (M v) when SnCl2
2H2O was used as a catalyst in the
polymerization. The molecular weight of PLA was not high
when Sn/Ti mixed oxide catalysts were used in this reaction
because they were very hydrophilic and had not proper
Lewis acid sites generated from Sn–O–Ti ‘‘hetero-link-
age’’. In general, the thermal properties of PLA such as Tg
and Tm increased with the molecular weight. However,
when methoxybenzene was used as a solvent, as the poly-
merization proceeded, Tm decreased to 145 8C and the
intensity of exothermal peak decreased owing to the change
from L-form to D,L-form, partially through racemization
and interaction between the methoxy group in the solvent
and the reactant, where XRD results shows that PLA
crystallinity was lower.
Acknowledgement: This research was funded by ‘‘Center for
Ultramicrochemical Process Systems (CUPS)’’ sponsored by
KOSEF (2001) and ‘‘Bioprocess Engineering Research Center’’
(1999).
Received: November 29, 2001
Revised: February 18, 2002
Accepted: March 29, 2002
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