The Basic Properties of Poly(lactic

Acid) Produced by the

Direct Condensation
Polymerization of Lactic Acid
By:
M. Ajioka, K. Enomoto, K. Suzuki, and A.
Yamaguchi
Journal of Environmental Polymer Degradation,
1995
Is presented:

Abstract
Poly(lactic acids) with high molecular weights have been synthesized by

direct condensation polymerization of lactic acid. These polymers have

good mechanical properties and can be processed into products such as
cups, film, and fiber, which can be used as compostable materials. This
polymerization method can be applied to the synthesis of copolymers of
lactic acid and other hydroxyacids. The properties of poly(lactic acid)
and copolymers synthesized by the direct process are different from
those of polymers obtained by the conventional lactide process

Introduction
Large amounts of plastics are produced worldwide, and disposal of plastics
after use is becoming a serious problem. About 70% of general waste is
incinerated in Japan.
To solve these problems, several types of degradable polymers, such as
blend of starch, PVA, PHB, and PLA have been developed.
Polylactic acid or polylactide (PLA) has been acknowledged as having a
good potential for biodegradable packaging and consumer goods because
of its good properties, such as mechanical strength, transparency,
compostability, and safety

Cont.. Introduction
The

raw

material,

fermentation

of

lactic

acid,

carbohydrate

is

produced

from

by

renewable

resources, such as corn. In the USA, PLA is $2/kg.

PLA has been produced by a multistep process including
a production and an isolation of intermediate lactide,
the cyclic dimer of lactic acid, followed by its ringopening polymerization

State of the art

(S. Sakura et. al, 1964) and (Y. Ikada, et. al., 1984) do the
research about the direct condensation process for many
years but no one has ever succeeded in obtaining a
poly(lactic acid) with a high enough molecular weight and
useful properties because of the equilibrium between free
acids, water, and polyesters and the viscous polyester
melt, causing difficulty in removing by-produced water.

Novelty:
We studied the direct process with two interests:
Academic: Aliphatic polyesters such as PLA with high
molecular weights have not yet been successfully
produced through direct condensation polymerization
Industrial: The conventional lactide process consists of
multiple steps and highly purifed polymer-grade lactide
is required to obtain a PLA with a high molecular weight.

Biopolymer
: PLA

Production scheme of PLA via direct and lactide process

Materials
Heat-stable-grade L-lactic acid was purchased as a 90 wt

% aqueous solution from Purac Co.

Aqueous

solutions

of

70%

glycolic

acid

and

e-

caprolactone were purchased from Tokyo Kasei Kogyo

and Aldrich Chemical Company, respectively.
L-Lactide was purchased from Boehringer Ingerhime.
All of the solvents were obtained from commercial

sources Molecular sieves

Experimental
The molecular weights were determined by gel permeation chromatography (GPC) on a
Shodex GPC System-I 1 (Showa Denko)
The glass transition temperatures (Tg) and melting points (Tm) were measured with a
differential scanning calorimeter (Shimadzu DSC-50)
The tensile measurements were made using an Orientec Tensilon UCT-1T 1122 at room
temperature according to ASTM D638
The decomposition temperatures (To) were determined on a Shimadzu TGA-50
thermogravimetric analyzer (TGA)
The melt viscosities were measured on a Rheometrics dynamic spectrometer
(Rheometrics Inc., RDS II)
The melt flow rates were determined on a Toyo Siki melt indexer.

General Procedure for the Synthesis of Poly lactic Acid (Direct Process)

Azeotropically
400 ml organic
solvent

(3 Amstrong)

0.1 gram

dehydration process

Molecular Sieve

hours

at 140 oC

20

catalyst

hours
130 oC

40.2 gram 90%

L-lactic acid

White powders
of

PLA

in

yield 80 85%

Powders of PLA
+

a
900

ml

methanol

40

gram

molecular
+

of
300

ml

chloroform

of

40
at

General Procedure for the Synthesis of Polylactide (Lactide Process)

0.03

wt%

was deaerated under

vacuum for
2 h and replaced by
nitrogen gas

Heated and stirrer

3 hours at 200 oC

lauryl alcohol
0.01

wt%

stannous octoate

216 gram (1.5

mol) L-lactide

Stirrer

Result and
Discussion:
Polymerization

Result and
Discussion: Molecular
weight of catalyst

Result and Discussion:

Flow Diagram Direct
Process of PLA

Result and
Discussion: Physical
Properties of PLA

Result and
Discussion:
Tensile strength
and Ultimate
Elongation with
different Mw of
PLA

Result and
Discussion:
Meat flow rate
with different
Mw of PLA

Conclusion
A poly(lactic acid) with a Mw higher than 300.000 was obtained
by direct condensation polymerization of lactic acid in the
presence of a catalyst and an organic solvent.
The direct process can be applied to the synthesis of
copolymers of lactic acid and other hydroxyacids.
The properties of poly(lactic acid) and copolymers synthesized
by our direct process are different from those of polylactide
and copolymers obtained by the conventional lactide process.