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Melt–solid polycondensation of lactic acid and its biodegradability

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 Progress in Polymer Science 34 (2009) 99–124

Contents lists available at ScienceDirect

Progress in Polymer Science

journal homepage: www.elsevier.com/locate/ppolysci

Melt–solid polycondensation of lactic acid and its biodegradability

T. Maharana a , B. Mohanty b , Y.S. Negi a,∗
a
Polymer Science and Technology Program, Department of Paper Technology, Indian Institute of Technology Roorkee, Saharanpur Campus,
Saharanpur 247001, Uttar Pradesh, India
b
Department of Chemical Engineering, Indian Institute of Technology Roorkee, Roorkee 247667, Uttarakhand, India

a r t i c l e i n f o a b s t r a c t

Article history: Sequential melt–solid polycondensation of lactic acid (LA) produces high molecular weight
Received 1 September 2007 (MW) poly(lactic acid) (PLA), which is cost effective and can be put to a variety of uses,
Received in revised form 8 October 2008
including packaging, biomedical and electrical appliances. This paper deals with the tech-
Accepted 8 October 2008
nology available for melt as well as solid state polycondensation of LA, the selection of
Available online 6 November 2008
catalysts, different synthetic methods, the effects of operating parameters on the MW of the
product, and various properties of PLAs such as their physical, thermophysical, mechanical,
Keywords:
Thermophysical properties electrical properties, degradation behavior and the dependence of these on the molecu-
Mechanical properties lar weight. The kinetics and mechanisms involved in the different synthetic methods and
Degradation degradation of the polymer are also discussed. Finally, a response optimization analysis
Design of experiment used in the design of experiments (DOE), suggests a group of parameters under which one
Solid-state polycondensation can achieve higher MW PLA, and provides mathematical relationships between synthesis
parameters and the MW.
© 2008 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
2. Raw material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
3. Structure of PLA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
4. Synthesis routes for PLA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
4.1. Ring opening polymerization (ROP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
4.2. Polycondensation (PC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
4.2.1. Mechanism of polycondensation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
4.2.2. Post-polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
5. Commercial production of PLA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
6. Properties of PLA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
6.1. Physical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
6.2. Thermophysical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
6.3. Electrical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
6.4. Mechanical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
6.5. Degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
6.5.1. Thermal degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
6.5.2. Degradation by radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
6.5.3. Biodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112

∗ Corresponding author. Tel.: +91 132 2714006; fax: +91 132 2714011.
E-mail addresses: dr yuvrjas negi@yahoo.co.in, ynegifpt@iitr.ernet.in (Y.S. Negi).

0079-6700/$ – see front matter © 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.progpolymsci.2008.10.001
100 T. Maharana et al. / Progress in Polymer Science 34 (2009) 99–124

7. Melt–solid polycondensation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114

7.1. Key steps leading to PLA synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
7.1.1. Dehydration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
7.1.2. Esterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
7.1.3. Decompression . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
7.1.4. Melt polycondensation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
7.1.5. Heat treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
7.1.6. Solid-state polycondensation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
7.2. Selection of catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
7.3. Kinetics and reaction mechanism of sequential melt–solid polycondensation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
8. Suggestions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
9. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120

1. Introduction
Nomenclature
Poly(lactic acid), PLA, is a biodegradable, biocompat-
ible and compostable polyester derived from renewable mm Hg(abs) Millimeters of mercury measured as
resources such as corn, potato, cane molasses and beet absolute pressure
sugar. It has a bright future as an environmentally friendly Da Dalton
Hm ◦ Melt enthalpy
thermoplastic. With the help of this green polymer indus-
tries will be able to close the carbon cycle, and their Mw Weight average molecular weight
dependence on non-renewable fossil resources will be Mn Number average molecular weight
reduced considerably. Mv Viscosity average molecular weight
Aliphatic polyesters such as PLA, derived from LA kPa Kilopascal
produced from renewable resources, has promising MPa Megapascal
applications in packaging, consumer goods, fibers and Tg Glass transition temperature
in biomedicine because of its excellent mechanical Tr Reaction temperature
properties, transparency, compostability and bio-safety. Tm Melting temperature
Earlier, polymers such as poly (␧-caprolactone) (PCL), Tc Crystallization temperature
polyhydroxybutyrate-valerate (PHBV), polyurethane (PU), LA Lactic acid
polyethylene (PE), poly(vinyl chloride) (PVC), polystyrene LLA l-lactic acid
(PS) and cellulosics were used for similar applications. OLLA Oligo(l-lactic acid)
Whereas, PLA was introduced in the market for medical PLA Poly(lactic acid)
sutures around 1968, its counterpart PHBV was introduced PLLA Poly(l-lactic acid)
much later, in 1983. PDLA Poly(d-lactic acid)
Commercially, PLA is synthesized using ring open- PDLLA Poly(d,l-lactic acid)
ing polymerization (ROP) of lactide monomer, obtained PC Polycondensation
through dimerization of LA, as well as by polycondensation ROP Ring opening polymerization
(PC) of LA as shown in Fig. 1. These methods of synthesis MW Molecular weight
due to their inherent weaknesses [1–7] increase the pro- PCL Poly(␧-caprolactone)
duction cost substantially. Table 1 lists some merits and PE Polyethylene
demerits of these methods of synthesis. To avoid of the PHBV Polyhydroxybutyrate-valerate
drawbacks, many investigators [1–7] have suggested alter- PVC Poly(vinyl chloride)
nate synthesis routes such as melt polycondensation and PU Polyurethane
sequential melt–solid polycondensation. Of these routes, PS Polystyrene
melt polycondensation followed by solid-state polycon- P(TMC-co-CL) Poly(trimethylene carbonate-co-␧-
densation with a suitable catalyst, offers high molecular caprolactone)
weight PLA with high yield in comparison to the ROP P(Cl-co-VL) Poly(␧-caprolactone-co-␦-
route. Many investigators [2,3,7–9] have synthesized high valerolactone)
molecular weight PLA by adopting a post polycondensation TDMA Temperature modulated dynamic mechan-
method. Of various post polycondensation methods, solid- ical analysis
state polycondensation (SSP) is preferred, as it does not TNBT Titanium(IV) butoxide
require any external agent during polymerization and thus
yields pure PLA. In addition, it provides higher MW as well
as higher yield in comparison with melt polycondensation. lar sieves to adsorb water produced by polycondensation,
However, some investigators have used food grade cata- thereby enhancing the rate of polymerization.
lysts like tin and organotin compounds such as stannous The number of steps suggested, in the melt–solid poly-
octanoate, as well as water tolerant catalysts and molecu- condensation process for the synthesis of PLA, by different
 T. Maharana et al. / Progress in Polymer Science 34 (2009) 99–124 101

centre. LA can be produced by fermentation from renew-

Fig. 1. Production scheme of PLA through PC and ROP.
investigators varies appreciably, being as high as 7. It may
take about 60 h for the production of PLA having a MW of
5 × 105 Da. The biodegradability of PLA has been studied by
many investigators [10–16] and it has been concluded that
it mainly depends on the MW. Based on the above backdrop,
it appears that a holistic approach should be undertaken
for the synthesis of PLA by integrating the knowledge base
already available for this purpose and a plan for synthesis
of high MW PLA should be developed. The present paper
meets this objective.
2. Raw material
Potential feedstock for the production of PLA is lactic
acid (2-hydroxy propionic acid), which contains a chiral
able resources such as milk and carbohydrates such as corn,
potato, cane molasses and beet sugar. The LA produced
contains both D and L forms, though the l-form is predom-
inant. l-lactide monomer, a cyclic dimer of LA, is currently
being distilled from corn biomass, which naturally contains
l-lactic acid, oligo(l-lactide) and other precursors which
are driven to cyclic l-lactide during the distillation pro-
cess. As a rough estimate, in the distilled product, l-lactic
acid can be present as high as 90 to 99%. The 90% pure
commercial grade lactic acid contains impurities such as
arsenic (<1 ppm), iron (<5 ppm), heavy metals (<5 ppm),
chloride (<10 ppm), sulfates (<10 ppm), sulfated ash (max-
imum 0.05%), reducing sugar, methanol and methyl ester.
Stereochemical purity of the raw materials (lactic acid) is
an important factor in deciding the properties of PLA.
3. Structure of PLA
The structural formula of PLA is shown in Fig. 2. It is a
chiral polymer in which molecules containing asymmet-
ric carbon atoms have a helical orientation. Two optical
isomers, PLLA and PDLA, exist in PLA. In 1968, de Santis
and Kovacs [17] reported the pseudo-orthorhombic crys-
tal structure of PLLA [18]. The crystal structure (Fig. 3) was
found to be a left-handed helix conformation for the ␣-
form. While drawing fibers of high molar mass PLLA, at
high draw ratio, a partial modification of the ␣-form to a
stable ß-form takes place [19]. Recently, a ␥-form has also

Table 1
Pros and cons of different methods employed for the synthesis of PLLA.

Principles Methods Advantages Disadvantages

ROP Solution polymerization
Bulk polymerization
Suspension polymerization
(i) Chemistry of the reaction can be accurately
controlled thus the properties of the resultant
polymer can be varied in a more controlled
manner
(ii) Mw varies from 2 × 104 to 6.8 × 105 Da
(i) Higher cost of production due to the
complicated purification process of the lactide
(ii) Azeotropic distillation of solvent used
(iii) High cost prevents commodity applications

PC Solution PC (i) High Mw can be achieved (i) Hard to remove solvent completely from the
end product
Bulk PC Provides low production cost (ii) Substandard mechanical properties
Melt PC (iii) Competitive reaction of lactide formation
and simultaneous degradation process at high
temperature
(iv) Difficulty in driving the dehydration
equilibrium to the direction of esterification
(v) Use of solvents results in complex process
control, leading expensive PLLA
(vi) Inability of formation of PLLA with a
sufficiently high molecular weight
(vii) Severe increase in melt viscosity
(viii) Byproducts are formed

Post PC Melt modification (i) High Mw can be achieved (i) May require external agent (example water
tolerant catalyst and molecular sieve)
Solid state PC (ii) Simple process (ii) Purification of lactide
Radiation (iii) Low investment (iii) Low reaction rate
(iv) Low cost of the operation (iv) Solid particle processability problems
arising from sintering
(v) Easy handling
(vi) Suppression of undesirable side reactions
and hence produces higher purity polymers
(vii) Cross linking increases heat resistance
(viii) Less energy requirement

Mw : wt. average MW.

102 T. Maharana et al. / Progress in Polymer Science 34 (2009) 99–124
Fig. 2. Structural formula of PLA, chiral molecule.
been obtained by epitaxial crystallization of PLA in hex-
amethylbenzene [20]. The crystal structure of PLA is based
on an orthorhombic-base-centered unit cell that contains
two 10/3 helical chains arranged along the c axis [21,22] as
Fig. 3. PLLA crystal structure projected onto (1 1 0) and (0 0 1);
orthorhombic system; point group D2 ; 10/3 helical chain; a = 1.06 nm;
b = 0.61 nm; c = 2.88 nm [21].
shown in Fig. 3. PLA shows hexagonal packing. The point
group of PLLA crystal is D2 . However, the structure of PLA
has not been completely established. Different investiga-
tors [17,20–22] suggest different parameters of the unit
cell.
4. Synthesis routes for PLA
Raw LA is purified by removing impurities, dehydrated,
and then polymerized. The presence of an asymmetric cen-
ter in LA helps in the formation of different enantiomers
such as PLLA, PDLA or PDLLA or a combination of these.
Polymers derived from LA by PC are referred to as poly-
lactic acid whereas; those from lactide by ROP are termed
polylactide. However, in common terminology both these
products are called PLA. At present there are two estab-
lished routes for the synthesis of PLA from monomer, LA.
These are: ring opening polymerization (ROP) and poly-
condensation as shown in Fig. 1. A further subdivision of
above synthesis routes is shown in Fig. 4. In ROP, the poly-
merization can be through cationic, anionic, coordination
or free radical polymerization whereas, in PC, condensa-
tion polymerization takes place by the elimination of small
molecules such as water.
4.1. Ring opening polymerization (ROP)
Using ROP, it is possible to control the chemistry of
polymerization accurately, and thus, the properties of
resulting polymer can be varied to suit the application.
High molecular weight PLLA is produced commercially,
by ROP of l-lactide obtained by decomposition of low
molecular weight PLLA. The ROP route includes PC of LA fol-
lowed by depolymerization to the dehydrated cyclic dimer,
lactide (3,6-dimethyl-1,4-dioxane-2,5-dione), which then
undergoes ROP to produce high molar mass PLA. The
depolymerization is done conventionally by simultane-
ously lowering the pressure to ≤266.6 Pa, maintaining the
temperature between 150 ◦ C and 220 ◦ C, and then distilling
off the produced lactide.
Because there are two stereo forms d-LA and l-LA, the
optically active lactide can be found in three different
stereoisomers: i.e. d,d-lactide, l,l-lactide and d,l-lactide
(meso-lactide) [23]. The composition of the polymer, in
terms of these stereoisomers, affects the properties of the
polymer [24,25].
Some of the leading producers of PLA like Cargill Dow
(Nature Works LLC), Shimadzu and Dupont are producing
PLA of varying molecular weight by ROP. The ROP of lac-
tide with Sn(Oct)2 catalyst with catalyst concentration of
100–1000 ppm gives PLA having molecular weights up to
106 Da at 140–180 ◦ C in 2–5 h [26].
ROP has been carried out by solution polymerization,
bulk polymerization, melt polymerization and suspension
polymerization [27]. The mechanism of polymerization
involved in ROP can be of ionic-, coordination- or free
radical-type depending on the catalyst used [28,29]. The
ROP of lactide is catalyzed by compounds of transition and
non-transition metals such as tin [30–34], lead [35], zinc
[36,37], bismuth [35], yttrium [38], iron [39], aluminum
[40,41] and magnesium [42]. Of these, tin(II) compounds
 T. Maharana et al. / Progress in Polymer Science 34 (2009) 99–124 103

Fig. 4. Different methods for PLA production.

are frequently used and are considered to be most efficient
[1,2]. The mechanism, of tin(II) 2-ethylhexanoate, involves
a pre-initiation step in which it is converted to a tin(II)
alkoxide by reacting with an alcohol. Then the polymer-
ization proceeds on the tin–oxygen bond of the alkoxide
ligand [33]. The highly active catalysts prepared using tin
compounds are toxic [43]. However, other tin compound
based catalysts such as organotin compounds and stannous
octanoate exhibit low toxicity. Low environmental impact
catalyst such as oxides of titanium (titanium(IV) butoxide)
have also been developed for lactide polymerization [44].
The presence of catalyst in the synthesized polymer
varies from as low as 9 ppm to a few hundred ppm. Further-
more, synthesized polymers also contain some unwanted
residual monomer which should be removed from the poly-
mer. The process of purification and isolation of l-lactide
from PLA makes it high-priced and thus prevents its appli-
cations as a commodity material. Although ROP produces
high MW PLA with high yield, it has also some disadvan-
tages, as shown in Table 1.
4.2. Polycondensation (PC)
Polycondensation of LA in the presence of catalysts
yields PLA and water as a byproduct. It has been observed
that binary catalysts, comprising of metal compounds
activated with proton acids, are more effective than
single-metal-compound based catalysts [1]. Binary cata-
lysts produce PLA of the order of ca. 105 Da with yield as
high as ca. 98%. PLA formed by PC of lactic acid consist
mainly of lactyl units. Such polymer is either composed of
one stereoisoform of two or a combination of both in var-
ious ratios [45]. One of the disadvantages, for the direct
PC, is that a low molar mass polymer showing substan-
dard mechanical properties is usually obtained, owing to
severe increase of melt viscosity and higher operating tem-
perature. Until 1995, it was believed that a high MW PLLA
could not be achieved by the direct polycondensation of
LA owing to inherent difficulty in driving the dehydration
equilibrium in the direction of esterification—which is a
requirement for the formation of sufficiently high molecu-
lar weight PLLA.
To overcome this difficulty, direct polycondensation of
LA to a high molar mass is obtained by manipulating the
equilibrium between LA, H2 O and PLA by using either
an organic solvent [46,47] or a multifunctional branching
agent (e.g. dipentaerythritol) [4,6,48]. A multifunctional
branching agent leads to a star-shaped polymer [49]. How-
ever, use of solvents such as diphenyl ether demands
complex process control leading to an expensive PLLA. It
is also difficult to remove solvent completely from the end
product. In an effort to avoid these difficulties, a new pro-
cess, called melt polycondensation has been developed for
obtaining a high molecular weight PLLA at reduced cost
[1,50]. Polycondensation of LA can also be done in the
presence of difunctional monomers (e.g. diols or diacids),
giving rise to telechelic prepolymers [51]. The telechelic
prepolymers thus produced, are used to yield a high molar

Table 2
Overview on different LA based polymers prepared by direct PC or by PC and chain extension [6].

Monomer Linking agent Macromolecular architecture Molecular size Reference

LLA – Linear homopolymer A, B [53,54]

LLA – Linear homopolymer B, C [1–4,55]
LLA HMDI Linear homopolymer C [46,56]
LLA Dipentaerythritol Star-shaped homopolymer C [34]
rac-LA – Random 50/50 stereocopolymer A [53,57]
rac-LA Dipentaerythritol Random 50/50 stereocopolymer C [58]

HMDI: hexamethylenediisocyanate; A: low molar mass polymer (<20 kDa); B: medium molar mass polymer (20–70 kDa); C: high molar mass polymer
(>70 kDa).
104 T. Maharana et al. / Progress in Polymer Science 34 (2009) 99–124
Fig. 5. Hypothetical condensation mechanism by the action of the Sn(II) and Sn(II)–TSA systems [1].
mass polymer through a second reaction step, involv-
ing a linking molecule such as diisocyanate [46,48] or
bis(amino-ether) [52]. These polymers show similar behav-
ior to poly(lactide) homopolymers prepared by ROP. Table 2
presents an overview of the different lactic acid based
polymers prepared by polycondensation and also provides
references on different aspects of structure and properties
of these polymers [6].
4.2.1. Mechanism of polycondensation
Though the effect of TSA on the polycondensation mech-
anism is not yet well understood, a plausible mechanism
has been proposed by Moon et al. [1]. The mechanistic
aspects are shown in Fig. 5.
1. Terminal groups of PLLA form coordinate bonds with the
catalyst center of Sn(II), present on tin(II)-oxide clus-
ter(2), formed by hydrolysis of SnCl2 ·2H2 O. Hydroxyl and
carboxylate ligands present in PLLA are responsible for
dehydration with the formation of Sn–OH (3).
2. The amounts of both terminal hydroxyl and carboxyl
group decrease with the increasing molecular weight of
PLLA. When the molecular weight of the PLLA becomes
high enough, the coordination sites of the catalyst center
are not filled with the terminal groups (3). The catalyst
site with this ligand vacancy induces side reactions, such
as the decomposition of l-lactide, causing discoloration
and racemization of PLLA. In fact, the reaction of l-lactide
with the catalyst at high reaction temperature causes
serious discoloration.
3. The proton acid added to the catalyst works as a ligand
for the catalyst site (4). As the proton acid is not involved
in the esterification, it fills the open coordination sites of
the catalyst to prevent side reactions. Addition of a strong
proton acid like TSA also stimulates the dehydration of
Compound 3 to 5 via 4, as shown in Fig. 5, and thereby
increases the rate of reaction.
A detailed analysis is needed for confirmation of these
mechanistic features of the melt polycondensation in
which a high molecular weight PLLA (ca. 105 Da) can
be obtained by the catalysis of tin(II) chloride dihydrate
with an equimolar amount of TSA within 35 h under
0.13–2.66 kPa pressure and within a temperature range of
180–200 ◦ C with an average yield of 67%.
If the mole ratio of TSA w.r.t. catalyst is too high, the
catalyst activity is hindered. This may be attributed to the
decrease in the number of vacant sites that are available for
the coordination of the polymer tails. During the polycon-
densation reaction, under the rigorous reaction conditions,
it appears that TSA evaporates from the reaction mixture
to induce side reactions such as racemization and discol-
oration. Discoloration of the product has been a serious
problem in the polycondensation of PLLA. During polycon-
densation, the color of PLA first changes to yellow, then
to brown, and finally it became black. This discoloration
may be due to various factors, such as, high reaction tem-
peratures, long reaction times, catalyst used, solvents and
byproducts. It has been observed that with the addition
of TSA, the product discoloration is effectively prevented
and the growth rate of the molecular weight is greatly
enhanced.
Polycondensation of LLA in bulk has been known to pro-
duce PLLA with molecular weight of order of only 104 Da
due to the unfavorable reaction equilibrium constant [59].
As the low molecular weight PLLA, thus produced, is too
brittle to be used as a useful material, increase of the
molecular weight is imperative. Solution PC of LLA also
yields high molecular weight PLLA, as obtained by ROP,
by using a large volume of solvent compatible with PLLA
[60,61]. Solvents with high boiling point such as p-xylene
and diphenyl ether, o-dichlorobenzene, o-chlorotoluene
are used for the removal of the dissociated water by
azeotropic distillation [59,62]. Polycondensation of LA
involves two reaction equilibria, namely, dehydration equi-
librium for esterification and ring-chain equilibrium for
depolymerization of PLLA into l-lactide as shown in Fig. 6.
Multiple reactors and complex facilities are needed for
these processes and thus invariably increase the produc-
tion cost of PLLA. Moreover, flammability and toxicity
 T. Maharana et al. / Progress in Polymer Science 34 (2009) 99–124
Fig. 6. Two reaction equilibria involved in polycondensation [1].
of the solvents make the solution process less attrac-
tive.
4.2.2. Post-polymerization
The low molecular weight PLA obtained by PC or ROP
can be processed further by various post-polycondensation
methods, e.g. melt modification, radiation induced cross-
linking and solid-state PC, to obtain high molecular weight
PLA. Melt modification has also been applied to PLA
obtained from ROP. Grafting and blending are two other
post-processing methods for PLA to produce heteropoly-
mers [6,45]. The PLA, obtained after polycondensation
or ROP, forms a homogeneous supercooled state with a
monomer ratio more than 5 wt%. During the post polymer-
ization process, crystallization of PLA occurs. In addition,
the monomer consumption reaches 100% as the monomer
and catalyst are concentrated in the amorphous part.
4.2.2.1. Melt modification. Structural melt modifications of
polymers are often related to radical reactions, which can
be generated by peroxides [63] or by high-energy radiation
[64]. Peroxide melt-modification of poly(␧-caprolactone)
(PCL) has been investigated in a number of studies [65–67]
and it has been found to undergo reactions resulting
in branching and cross-linking by use of 0.05–3 wt%
dicumylperoxide [66]. Peroxide melt-modification of PLA
causes drastic changes in a number of properties of the
polymer. Branching has been suggested to be the dom-
inating structural change in PLA at peroxide contents in
the range of 0.1–0.25 wt% and also cross-linking at perox-
ide additions above 0.25 wt% [68]. The peroxide reaction
increases the melt strength [69]. Morphological changes
occurred in the peroxide modified PLA because of reduced
crystallization rate and thus result in a hydrolytic degra-
dation [11]. Further, the tensile modulus is reduced and
a more flexible material is obtained [68,69]. Benzoyl per-
oxide stabilizes the polymer against thermal degradation
by deactivating the catalyst residues. The melting point of
the stabilized polymer decreases with increasing benzoyl
peroxide concentration.
4.2.2.2. Radiation induced cross-linking. PLLA was irra-
diated using an electron beam (EB) in the presence of
polyfunctional monomers (PFMs) such as triallyl iso-
cyanurate (TAIC), trimethallyl isocyanurate (TMAIC),
trimethylolpropane triacrylate (TMPTA), trimethylol-
propane trimethacrylate (TMPTMA), 1,6-hexanediol
diacrylate (HDDA), ethylene glycol, bis[pentakis(glycidyl
allyl ether)]ether, and hydroxyl terminated ethylene glycol
(EG), as cross-linking agents. The PFM, triallyl isocyanurate
105
(TAIC) at 3% concentration was found to be most effective
for cross-linking of PLLA by irradiation. Cross-linking of
PLA, by high-energy radiation, increases the degree of
cross-linking as a function of radiation dose and manip-
ulates the mechanical properties of PLA, affects the heat
resistance and reduces the solubility [8]. Cross-linked
PLLA is transparent and has heat resistance above 200 ◦ C.
It is used for heat-shrinkable tubes, cup and plates. An
unirradiated cup has been found to deform and became
translucent whereas, the cross-linked PLLA cup retains its
original shape and transparency even after boiling water
is poured into it. Because of the cross-linked structure of
PLLA the process of crystallization is inhibited and heat
resistance is improved. Thus, cross-linking is beneficial in
expanding the applications of PLLA.
Irradiation effects on aliphatic polyesters were studied
by D’Alelio et al. [70] in the late 1960s. Accounts of radical
induced modification of copolymers of lactide and other
ring-form monomers have not been found in the litera-
ture. It has also been seen that radiation has no effect on
Tg , Tm and rate of hydrolytic degradation. Tensile modulus
and tensile strength of PLA decrease upon irradiation [6].
Irradiation of PLA causes mainly chain-scission at doses
below 250 kGy [71,72]. At higher doses, cross-linking of
polymer chains increases as a function of the irradia-
tion dose, both in air as well as in an inert atmosphere
[72]. In air and nitrogen, and on irradiation with ␥-
rays at room temperature, PLA undergoes chain scission,
cross-linking and decrease in crystallinity simultaneously.
For PLA homopolymers, irradiation causes a substantial
decrease in the tensile strength and thus makes PLA brittle
[73,74]. Similar observations were recorded for copoly-
mers of lactide, glycolide [75] and copolymers of lactide
and ␧-caprolactone [76]. As radiation induced reactions,
mainly take place in the amorphous phase of the poly-
mer, the degree of crystallinity which indirectly defines the
amount of amorphous phase present in the polymer, is an
important parameter [71]. Irradiation does not accelerate
the hydrolytic degradation of poly(l-lactide) [77], poly(d,l-
lactide) [73] and copolymers of glycolide and lactide [75].
Peng et al. [78] suggested a new route for the synthe-
sis of PLA by microwave radiation melt polycondensation:
i.e. placing the LLA in an auxiliary reaction medium
(SiC), increasing the system vacuum from 0.050–0.070 MPa
to 0.080–0.099 MPa and applying microwave irradiation
for 30–50 min. With this process they obtained a pre-
polymer of 3000–5000 Da determined on the basis of
viscosity-average molecular weight. They further mixed
the prepolymer with catalyst (SnCl2 ·2H2 O (0.3–0.50 wt% of
prepolymer) and p-TSA at a mole ratio of 1:0.5–2.0, and irra-
diated with microwaves for 2–5 min under normal pressure
followed by further irradiation for 25–50 min by microwave
power (500–550 W) under vacuum (0.085–0.1 MPa) to
obtain PLA with Mv of 40,000–60,000 Da. They did not pro-
vide structure–property correlation data for the PLA thus
produced.
4.2.2.3. Solid-state polycondensation (SSP). Although
Vouyiouka et al. [79] reviewed and discussed kinetics
and simulation of SSP of polyamides and PET they did
not discuss it for PLA. A limited amount of literature,
106 T. Maharana et al. / Progress in Polymer Science 34 (2009) 99–124
including patents, is available on post-polycondensation
of PLA [9,80–100]. However, a substantial amount of
work is available on SSP of PBT, PET, polyamides and
polycarbonates.
SSP appears to be an effective route for PLA synthesis
when compared with ROP and simple polycondensation.
The process comes under Green Chemistry: it is simple,
easy to handle, and because of the lower reaction tempera-
ture compared with melt polymerization, does not promote
undesirable side reactions. Further, high molecular weight
PLA can be synthesized by melt polycondensation fol-
lowed by SSP [81]. SSP involves both chemical and physical
steps. Since it is controlled by reaction kinetics, reactive
chain-end mobility in the amorphous phase and conden-
sate removal through diffusion are important issues. SSP
increases the degree of polymerization considerably, and
thus can increase the molecular weight of a polycondensate
up to 20 times [86].
In SSP, a semicrystalline solid prepolymer, of relatively
low molecular weight, in powder, pellet, chip or fiber
form is heated to a temperature below Tm but above Tg
(to improve mobility and subsequent reaction of the end
groups) in the presence of a suitable catalyst. Simultane-
ous removal of the byproduct of condensation from the
surface of the material is necessary, after it diffuses out
from the bulk, either by evaporation under reduced pres-
sure or by driving it away by a carrier gas. An optimum
amount of crystallinity is required to prevent agglomera-
tion of particles in the reactor [12,101,102]. SSP essentially
takes place in the amorphous region of the polymer, where
all the reactive end groups reside. Since SSP actually starts
at much lower temperatures, compared to polymerization
in the molten state or in solution [103], the reaction tem-
perature can range from sufficiently below Tm [104] to just
5–15 ◦ C above Tm [105]. The Tm of PLLA is ca. 175 ◦ C. This
is, therefore, also a high temperature reaction. Because of
the restricted and slow mobility of end groups, the time
needed to reach a particular molecular weight is generally
much longer than in the melt or solution [104]. SSP reduces
discoloration and degradation associated with high tem-
perature melt polymerization, thereby, making it useful in
polyester and polyamide synthesis.
Although, SSP takes a considerably longer time, very
high molecular weight PLLA can be obtained, which can-
not be accomplished in melt or solution polymerization,
owing to viscosity restrictions and hydrolytic, thermal and
oxidative degradation [106–108]. Almost all catalysts for
melt and solution phase polycondensation can be used as
catalysts for SSP [109,110].
Table 3
Plasticizers used and their effects.
Type of plasticizer Plasticizer
Renewable resource based plasticizers Citrate ester (tri-acetyl n-butyl citrate), tributyl
citrate glucose monoesters, glycerol, partial
fatty acid esters, oligomeric lactic acid
Biocompatible plasticizers Polyethylene glycol (PEG), PEG monolaurate
Multiple plasticizer Blends of low molecular weight triacetin (TAC)
and oligomeric poly(1,3-butylene glycol
adipate) (PBGA)
Moon et al. [3] obtained PLLA of 6 × 105 Da by melt–solid
polycondensation of LLA catalyzed by a SnCl2 ·2H2 O/p-TSA
binary system. They first prepared a polycondensate with
a molecular wt. of 2 × 104 Da by melt-polycondensation.
This product was heat treated around 105 ◦ C to promote
crystallization; and then it was heated at a temperature
somewhere within 140–150 ◦ C for 10–30 h for further poly-
condensation to produce PLLA of 6 × 105 Da. A high-quality
PLLA, with high yield of about 90% having a molecular
weight exceeding 5 × 105 Da, can be obtained within a rel-
atively short reaction time of about 40 h. The molecular wt.
of PLLA thus achieved is comparable with that obtained
by the lactide method using ROP. They further observed
that, the polycondensate obtained after heat treatment
does not show a crystallization exotherm in DSC, but does
show a clear melting endotherm at 158 ◦ C. The heat-treated
polycondensate did not melt up to 150 ◦ C, thus SSP was con-
ducted at 150 ◦ C for different lengths of time (10–30 h) to
obtain high polymer without discoloration. An optimum
amount of crystallinity is required to prevent agglomera-
tion of particles in the reactor [5].
Plasticizers can be used to increase the mobility of the
end groups in the amorphous region and consequently to
increase the rate of the SSP reaction. Polyethylene glycols
(PEG) of two different number average molecular weights
have been selected as plasticizers [111]. Although, citrate
esters, dimethyladipate, tributylcitrate, acetyltributylci-
trate and PCL are reported as biodegradable plasticizers
(Table 3) for PLA polymers [112–116], these should not be
used because they have aliphatic alcohol and ester groups
which can undergo transesterification with the PLA chain
ends. One of the crucial properties of a plasticizer is that it
should be miscible with PLA, so that a homogeneous blend
can be created by polar interactions. Further, the plasti-
cizer should not be too volatile because this could cause
evaporation to occur at the elevated temperature used dur-
ing processing. Furthermore, the plasticizer should not be
prone to migration because this could cause contamination
of materials in contact with the plasticized PLA. It could
also cause the blended materials to regain the brittleness
of pure PLA. Some problems faced during synthesis or with
synthesized polymer and their remedies are indicated in
Table 4. M/s Cargill uses low amounts of an epoxidized
natural oil to introduce branching into the polymer chain
during polymerization [113]. Branching achieved during
polymerization has the additional benefit of reducing melt
viscosity, which further assists in processing. Melt elasticity
and subsequent effects can be controlled by various tech-
niques such as controlling base PLA, comonomer, reactor
Effects Reference
Tg /Tm decreases and elongation at break [114]
increases
Flexibility and impact resistance improves; [115]
gains deformation and resilience
Tg /Tm decreases and elongation at break [116]
increases
 T. Maharana et al. / Progress in Polymer Science 34 (2009) 99–124 107

Table 4
Solutions to problems faced during melt–solid polycondensation.

Problem Solution Remark

Discoloration
Low MW
Poor melt elasticity leading to
problems during extrusion processes
Lactide formation at high temperature
Backward reaction occurs due to
formation of H2 O molecules during
condensation
Residual monomer
Addition of protonic acid like TSA as cocatalyst
which also enhances the rate of growth of
molecular weight
Polycondensation of lactic acid in presence of
water tolerant catalyst followed by solid-state
polycondensation in presence of molecular sieves
as water absorbents
Use of binary catalyst also enhances molecular
weight
The most promising method of increasing the level
of entanglement is by introducing branching into
the polymer
Branching agent like epoxidized natural oil and
cross linking agent like peroxides, can be used to
attain this
The reaction can be carried out at high temperature
and low pressure to overcome this problem
Water tolerant catalysts can be used. During solid
state polycondensation molecular sieves can be
used as water absorbents to enhance the reaction
rate
(a) Crystallization followed by SSP
(b) Polymerization temperature ∼ crystallization
temperature (Tc )
May be caused by various factors like high reaction
temperature, long reaction time, catalysts, solvents
and byproducts
Molecular sieve is represented by a chemical
formula [M(I),M(II)]O·Al2 O3 ·nSiO2 ·mH2 O, where
M(I) and M(II) are monovalent metal and bivalent
metal, respectively, which include Na, K, Ca, Sr, Ba,
n = 2–10, m = 0–9
Poor elasticity results from the low degree of
molecular chain entanglement
Low pressure increases the boiling point
Reaction rate is enhanced and the reaction
proceeds to formation of high MW PLA
(1) Polymer crystallization was induced during
polymerization to promote monomer consumption
to reach 100%
(2) Monomer consumption was found to reach
100% because the monomer and catalyst could be
concentrated in the amorphous part

configuration, initiator and cross-linker. As the polydisper-
sity index (PDI) of the polymer increases, the melt elasticity
increases.
Table 5 gives some input parameters of signifi-
cance, involved in melt polycondensation. Some progress
has recently been achieved in obtaining high molar
mass polymer by sequential melt–solid polyconden-
sation [2,7,44]. The advantages and disadvantages of
the different methods of synthesis are summarized in
Table 1.

Table 5
Variation of operating parameters on output variables during synthesis of PLA by melt polycondensation method.

Reference Input parameters Output variables Remarks

Amount of Time of Temp (◦ C) Catalyst Pressure (Pa) Monomer Yield % MW (Da)

monomer Rxn (h) used

[44] NA 40 180 Ti(OBu)4 133.3 l-LA NA 1.3 ×105 DP used

[50] NA 12 180 SnCl2 /p-TSA 1,333.3 l-LA 42 30,000 BC more
efficient. MP
used
Sn(II)Oct NA 45 19,000

[117] NA 10 170–180 SnCl2 (0.5 wt%) 70 (d,l)-LA NA 4,100 MP used

[118] NA 23 160 Sn(II)Oct NA (d,l)-LA 80 8.2 × 103 MP used

[119] 10 g OLLA <15 180 SnCl2 with 0.2% 1,333.2 l-LA 40,000 BC & MP used
Al(Oi Pr)3 13 2.7 × 104
Ti(Oi Pr)4 38 5.7 × 104
Y(Oi Pr)3 37 1 × 104
Si(OEt)4 78 2.2 × 104
Ge(OEt)4 -Best 65 3.7 × 104

[120] 30 g 24 100–220 NA NA (d,l)-LA NA 1 × 105 MP used

[1] 200 g <15 180 SnCl2 /p-TSA 1,333.2 LLA 67 1 × 105 BC and MP used

[121] 1000 ml 30 120–200 Sn(II)Oct 666.6–101,325 LA NA 1.6 × 104 MP used

Maximum at 0.05 wt%

[57] NA 1–7 200 No catalyst used NA (d,l)-LA NA Mn 3800 DP used

[55] 36.2 g 20–40 140 Sn powder (0.14 g) NA LLA NA 1.4 × 105 DP used

BC: binary catalyst; MP: melt polycondensation method; SP: solution polycondensation method; DP: direct polycondensation method; BP: bulk poly-
merization LA: lactic acid; TSA: toluene sulphonic acid; PBS: phosphate buffered solution; Da: Dalton; Sn(II)Oct: stannous octanoate; SSP: solid-state
polycondensation; Rxn: reaction; NA: not available.
108 T. Maharana et al. / Progress in Polymer Science 34 (2009) 99–124

Table 6
Industrial production of PLA.

Company name/location Trade name Production capacity Mw (Da) Mn (Da) Process used
(metric tons/year)

NatureWorks (Cargill/Teijin)/NB, USAa NatureWorks PLA 140,000 NA 1.22 × 104 (94% Solvent free
(Eco PLA) l-LA content)
Melt PC/ROP

Toyota (Shimadzu Co.)/Kyoto, Japan* LACTYTM 5000 >100 2.89 × 105 1.7 × 105 ROP
LACTYTM 2012 1.6 × 105 1.883 × 105 (100%
l-LA content)
Eco-plastic

Dupont/USAb Medisorb NA 1.0 × 105 NA ROP

Purac plc./Netherlands Purasorb® PL NA 3.5 × 105 1.5 × 105 ROP/

Solution PC

Mitsui Chemicals Co./Japanc LACEA 500 NA NA Solution PC

Birmingham Polymers/AL, USAd LACTEL NA NA NA NA
Toyobo/Japan Vyloecol NA 43 × 103 NA NA
Hisun Biomaterials Co. Ltd./Chinae REVODE 5,000 NA 70 × 103 NA

NA: not available; Mw : weight average molecular weight; Mn : number average molecular weight.
a
http://www.natureworksllc.com/corporate/nw pack home.asp.
b
http://www.lakeshorebiomaterials.com/about.html.
c
http://www.mitsui-chem.co.jp/e/.
d
http://www.birminghampolymers.com/.
e
www.plaweb.com.

Table 7
Mechanical properties of PLA.

Polymer Tg (◦ C) Tm (◦ C) Tensile strength (MPa) Tensile modulus (MPa) Flexural modulus (MPa) Elongation

Yield (%) Break (%)

l-PLA (MW: 50,000) 54 170 28 1200 1400 3.7 6.0

l-PLA (MW: 100,000) 58 159 50 2700 3000 2.6 3.3
l-PLA (MW: 300,000) 59 178 48 3000 3250 1.8 2.0
d,l-PLA (MW: 20,000) 50 – n/a n/a n/a n/a n/a
d,l-PLA (MW: 107,000) 51 – 29 1900 1950 4.0 6.0
d,l-PLA (MW: 550,000) 53 – 35 2400 2350 3.5 5.0

5. Commercial production of PLA a glass transition temperature in the range 55–60 ◦ C. It is

A number of industries are involved in the synthesis
of PLA by various methods. Before discussing the new
enhanced methods, employed for the production of PLA,
it will be interesting to analyze the commercial prod-
ucts, their methods of synthesis and product specifications.
The properties of the PLA, produced by these industries,
have been collected and analyzed, and are reported in
Tables 6 and 7.
There are also some other producers of PLA, such as
Kanebo Gohsen Limited/Australia (Lactron), Kaneka Cor-
poration/Japan/USA (Kanepearl PLA foam), Toyota Motor
Corporation/USA (Toyota Ecoplastics U’z series), etc., other
than those listed, which produce PLA in small amounts.
desirable that PLA should have some crystalline content as
it benefits the finished product, as shown in Table 8.
The degree of crystallinity depends on many factors,
such as molecular weight, thermal and processing history,
and the temperature and time of annealing treatments. The
meso- and d,l-lactide form atactic PDLLA which is amor-
phous. The mechanical properties and degradation kinetics
of the semicrystalline PLLA are quite different from those
of completely amorphous PDLA. Mechanical and thermal
properties of PLLA become almost constant when its molec-
ular weight is above a threshold value of 70,000 Da [119]. In
general, for a particular use, the mechanical, physical and
biodegradability properties of PLLA must be considered.

Table 8
6. Properties of PLA Crystallinity benefits [113].

Products Benefits
The thermal, mechanical and biodegradation properties
of PLA are largely dependent on the ratio and distribution of Fibers/non-wovens Improved heat set; chemical resistance; higher
strength
the two stereoisomers of LA within the polymer chains [18]. Cutlery Heat resistance; stiffness
Polymers with high l-isomer produce crystalline products Trays/cups Heat resistance; environment stress crack
whereas, the higher d-levels (>15%) result in an amorphous resistance (ESCR)
product. Thus, commercial PLLA products are semicrys- Films Blocking resistance; permeability; chemical
resistance
talline polymers with a high melting point ca. 180 ◦ C and
 T. Maharana et al. / Progress in Polymer Science 34 (2009) 99–124 109

Table 9 tion to those listed above. Non-solvents for lactic acid based
Physical properties of PLA produced by DURECT Corporation, Birmingham
polymers are water, and unsubstituted hydrocarbons.
Polymers, AL, USA.

Property l-PLA dl-PLA 6.2. Thermophysical properties

Glass transition temperature (Tg ) 60–65 ◦ C 50–60 ◦ C
Melting point (Tm ) 184 ◦ C Amorphous Thermophysical properties of PLA have been studied by
Specific gravity 1.24 1.25 various investigators using thermal analyzers such as TGA,
Tensile strength (MPa) 55.2–82.7 27.6–41.4
DTA, DSC and TDMA. The thermal analyzer can be coupled
Elongation (%) 5–10 3–10
Modulus (MPa) 2758–4137 1379–2758 with a mass spectrometer, NMR, HPLC, etc. to study the
Inherent viscosity (dl/g) 0.90–1.2 0.55–0.75 degradation products and kinetics of degradation.
Enantiomerically pure PLA, is a semicrystalline polymer
with Tg of about 55 ◦ C and Tm of about 180 ◦ C, whereas,
The properties of PLA and its copolymers, synthesized
polymers prepared from meso- or rac-lactide are in general
by the polycondensation, are not different from those of
amorphous and do not have a sharp melting point. Poly-
polymers obtained by the conventional lactide process [4].
mers having tacticity high enough for crystallization have
been obtained by using stereoselective catalysts [6]. The
6.1. Physical properties melt enthalpy estimated for enantiopure PLA of 100% crys-
tallinity is 93 J/g [124], the value most often referred to in
Physical properties of polymeric materials depend on the literature, although higher values (up to 135 J/g) have
their molecular arrangement as well as ordered struc- also been reported [125,126]. The Tm and degree of crys-
tures such as crystalline thickness, crystallinity, spherulite tallinity are dependent on the molar mass, thermal history
size, morphology and degree of chain orientation. For and purity of the polymer [127–129]. Crystallization kinet-
many products, crystallinity is a desirable property. For ics and melting behavior of PLAs of different optical purity
SSP of PLLA or PDLA single polymer, molecular weight have been investigated in several studies [25,130–135]. It
increases rapidly in comparison with block copolymer of has been observed that an optical purity of at least 72–75%,
PLLA and PDLA. Physical properties are very important as corresponding to about 30 isotactic lactyl units, is required
they reflect the highly ordered structure of the polymer and for crystallization to take place [24,136]. However, Sarasua
influence mechanical properties and their change during et al. [137] have been able to crystallize a poly(lactide) of as
hydrolysis. Some significant properties of PLA are given in low as 43% optical purity, using salen–Al–OCH3 (a complex
Tables 9 and 10 [122]. resulting by using a Schiff base on AlEt2 Cl) as an initiator for
The concept of solubility parameters was developed by polymerization. This is possible because of the formation
Scatchard and Hildebrand [123] on the basis of the theory of of long isotactic sequences. They reported that a sample, of
regular solutions. The Hildebrand solubility parameter ı at 47% optical purity, has Tm of 99 ◦ C (Hm = 18 J/g). Monodis-
a given temperature can be expressed as the square root of perse oligomers of 22 isotactic lactyl units prepared by
the cohesive energy Ev divided by the molecular volume fractionation have also been reported to crystallize, show-
V, i.e. the square root of the cohesive energy density [123]: ing a melting temperature of 59 ◦ C (Hm = 39 J/g) [138].
Ev Enantiomeric oligomers of a few lactyl units show a molar
ı= (1) mass dependent glass transition temperature. Values of
V
Tm , Tg and H are dependent mainly on the structure
The Hildebrand concept, in its most simplified form,
of PLA and molecular weight [139,140]. Thermal proper-
is used in terms of a progression, attaching one solu-
ties of PLA can be changed by copolymerization of PLA
bility parameter to each solvent or solute. Substances
with monomers such as glycolide, some lactone deriva-
with ı values of similar magnitude should be miscible
tives, trimethylene carbonate, etc.—and also by addition of
or soluble. Solubility, of lactic acid based polymers, is
cross-linkers [141–143] and plasticizers.
highly dependent on the molar mass, degree of crys-
tallinity and other comonomer units present in the polymer
6.3. Electrical properties
[6]. Chlorinated or fluorinated organic solvents, dioxane,
dioxolane and furane are found to be good solvents for
In order to apply PLA as an insulating material, for
enantiomerically pure PLA. However, PDLLA is soluble in
example, in electric wires and cables, it is necessary to
organic solvents such as acetone, pyridine, ethyl lactate,
study the basic electrical insulation properties: volume
tetrahydrofuran, xylene, ethyl acetate, dimethylsulfoxide,
resistivity, dielectric constant, dielectric loss tangent,
N,N-dimethylformamide and methylethyl ketone in addi-
impulse breakdown strength and storage of space charge,
at room temperature. The basic electrical insulation prop-
Table 10 erties of biodegradable PLA were measured by Nakagawa
Physical properties of PLLA [122].
et al. [21]. They measured the volume resistivity, dielectric
Mv Tm a (◦ C) Hm a (J g−1 ) Tg b (◦ C) Cp b (J g−1 K−1 ) constant, and dielectric loss tangent at room temperature
5,300 156 61 55 0.60 as given in Table 11. These were found to be comparable to
20,000 174 68 59 0.54 those of crosslinked polyethylene (XLPE), currently used as
691,000 186 59 64 0.54 insulating material for cables and electric wires [21]. The
a
By DSC, 10 K min−1 . dielectric constant of PLLA is higher than that of XLPE. One
b
By DSC, 20 K min−1 . reason for this might be the existence of a carbonyl group
110 T. Maharana et al. / Progress in Polymer Science 34 (2009) 99–124
Table 11
Electrical properties [21].
Material c-PLLA a-PLLA
Volume resistivity ( cm) 55 × 1016 49 × 1016
Dielectric constant 3.8 3.0
Dielectric loss 0.020 0.022
c-PLLA: degrees of crystallinity higher than 50%.
a-PLLA: degrees of crystallinity lower than 10%.
in the polymer chain of PLLA. The dielectric constant of
PVC, currently used for insulating electric wires, is 3.4, and
the dielectric constant of oil-immersed insulating paper
used for insulating high-electrical-field cables, is about
3.5. The dielectric constant of PLLA is smaller at about 3.0.
The current waveform of PLLA was recorded with an
oscilloscope by Nakagawa et al. [21]. They observed that
samples were destroyed when current was passed through
them. Further, they observed that the applied impulse
voltage increased when current did not flow through the
sample. They found the mean impulse breakdown strength
of PLA to be about 1.3 times higher than that of XLPE. They
measured the storage of space charge in XLPE and PLLA
by the pulsed electroacoustic method, with a dc electric
field applied to the sample and found that homocharge
mainly accumulates in the neighborhood of the anode after
electric charging although the amount of accumulation is
less than in XLPE [21]. The electric charge induced in the
anode of PLLA is compared with that of XLPE, with the
electrode grounded, after the applied field is switched off.
In this situation, the electric charge of PLLA is about 60%
that of XLPE. Although, the electrical properties of PLA have
been characterized, it requires thorough characterizations
for day-to-day use. PLA composites have been developed
recently for use in electronic products.
6.4. Mechanical properties
The mechanical properties of polymers of similar molar
masses, but prepared by different polymerization pro-
cesses, do not much differ. This has been noticed for
PLAs, prepared by both polycondensation and ROP [6].
The mechanical properties of PLA can be varied to a large
extent, ranging from soft and elastic plastics to stiff and
high-strength materials. Semicrystalline PLA is preferred
to amorphous polymer when better mechanical properties
are desired. The molar mass of the polymer [144–147] as
well as the degree of crystallinity [148,149] has a significant
influence on the mechanical properties. Semicrystalline
PLA of 30–38% crystallinity has a tensile modulus of approx-
imately 9.2 × 103 MPa and tensile strength of 870 MPa
[114,150–153]. It has been shown that tensile strength and
modulus of PLLA increase by a factor of 2 when the weight-
average molar mass is raised from 50 × 103 to 105 Da [145].
A further increase in molar mass to 3 × 105 Da does not
influence the properties of the polymers in any signifi-
cant way. The biomaterials tested, however, have different
degrees of crystallinity, which affects their properties [145].
Grijpma and Pennings [148] varied the crystallinity of PLA
by preparing stereo-copolymers with small amounts of d-
lactide and found maximum impact strength of 37 kJ/m2
when the copolymer had a Hm of 60 J/g, corresponding
to a crystallinity of 65%. In addition, a low degree of chain
XLPE entanglements occurred in highly crystalline material
46 × 1016
[154]. When the crystallinity of the PLA was reduced, the
2.4 density of chain entanglements increased, even though the
0.018 crystallinity was high enough to give physical cross-linking
and thus the material was not as brittle as amorphous
or low-crystalline material. Similar crystallinity dependent
impact strength results were also obtained when PLLA was
cross-linked with 2,4,7,9-tetraoxaspiro[5.5]undecane-3,8-
dione or 5,5 -bis(oxepane-2-one) [86,94,101,102]. Superior
mechanical properties have been achieved by stereocom-
plexation of enantiomeric PLAs, which was ascribed to
formation of stereocomplex crystallites giving intermolec-
ular cross-links [144].
The viscometric molecular weight of PLA decreases
when fibers are drawn from it by melt-spinning. Weight
loss of 90% occurred during extrusion and 10% during hot-
drawing [151]. PLLA of high molar mass has sufficient
strength for use as load bearing material in medical applica-
tions, but it degrades slowly because of the reinforcing crys-
talline domains [154,155]. The crystallinity can be reduced
by copolymerizing with d-lactide, leading to an amorphous
dl-PLA with a faster degradation profile [156]. Copolymer-
ization, however, will also reduce the toughness and impact
strength of PLA by a factor of 3 [157]. In order to enhance the
toughness of fast degrading amorphous PLA, modification
by blending and by block copolymerization has been sug-
gested [143,149,157–161]. A number of scientists have stud-
ied blends of PLLA with P(LLA-co-CL) rubber [161], P(TMC-
co-CL) or P(CL-co-VL) [157]. Blending improved impact
strength, an effect that can be attributed to phase sepa-
ration of the block segments in the copolymer [158,159].
Cross-linking also enhances the mechanical properties,
especially the impact strength. The influence of different
plasticizers (Table 3), e.g. lactide, on the mechanical proper-
ties of PLLA has been reported [114,150,162]. Jacobsen et al.
[162] found a linear dependence between residual lactide
in the PLLA and tensile strength at monomer conversions
exceeding 90%. When the polymer contained 10% residual
lactide the tensile strength of the PLLA was found to be 15%
lower than that for a PLLA with 97% conversion [162]. Gupta
et al. [163] presented a more detailed critical review of PLA
fiber. They discussed the structure-property relationship
of PLA fiber. Degradation of PLA can be studied either by
hydrolysis or by thermal methods. The various methods,
discussed here, can be classified as in Fig. 7. All of these
methods follow hydrolytic degradation.
6.5. Degradation
6.5.1. Thermal degradation
The degradation of polymers has been defined as the
number of chain scissions produced during a known period
and can be expressed by Eq. (2) [164]:
1 1
= + kD t (2)
DP DP 0
where DP0 and DP are, respectively, the initial and final
values of the average degree of polymerization, kD is the
degradation rate constant and t is time. This equation
 T. Maharana et al. / Progress in Polymer Science 34 (2009) 99–124
Fig. 7. Different biodegradation methods for PLA.
is valid for condensation polymers when the amount of
broken bonds is low, i.e., kD t  1. The degree of depolymer-
ization can be monitored by the average molar mass as a
function of the degradation time. As the viscosity of a poly-
mer solution or a melt can be related to the average molar
mass, the degree of polymerization can be correlated with
the viscosity changes as given by
1 1
= + kD t (3)
(0,t )˛ (0 )˛
where the exponential factor ˛ depends on molar mass and
melt viscosity and is a constant equal to 0.294 for molar
masses above the critical molar mass [165]. Eq. (3) is valid
for polymer melts for degradation by random main-chain
scission [166].
For PLA, most of the degradation reactions were consid-
ered to involve highly concentrated ester bonds on the main
chain. These reactions include thermohydrolysis, depoly-
merization, cyclic oligomerization and intermolecular and
intramolecular transesterification. Low molecular weight
compounds associated with the polymer and the hydroxyl
end groups of the main chain seem to play an important
role in lowering the molecular weight at high temperatures.
An increased amount of polymerization catalyst in the
end product also catalyzes the degradation reactions [127].
The degradation compounds include water, monomers,
oligomers, and polymerization catalysts. Removal of the
non-polymeric contents and blocking the hydroxyl end-
groups enhanced the thermal stability of PLA. The thermal
degradation was found to proceed by random main-chain
scission.
Benzoyl peroxide was found to stabilize the polymer
against thermal degradation by deactivating the catalyst
residues. The melting point of the stabilized polymer
decreased with increasing benzoyl peroxide concentration
[167]. The presence of oxygen is significant for the stabiliza-
Table 12
Influence of the peroxide addition and polymer purification on the degradation rate constants during 10 min of melt mixing at about 190 ◦ C [166].
Polymer Tin content (mg/g of PLLA)
PLLA base polymer 0.69
PLLA + 0.05 mol% t BuO2 Bz 0.69a
PLLA + 0.05 mol% t BuO2 Bz 0.69a
Precipitated PLLA 0.49
Purified PLLA 0.18
Purified PLLA + 0.08 mol% t BuO2 Bz 0.18a
a
Assumed to be equal to the unmodified.
111
tion of PLLA with peroxides. However, the degradation rate
constant for the PLLA modified with di-tert-butyl perox-
ide was less than that for the unmodified PLLA determined
under similar conditions. It seems that access to oxygen
was limited but not excluded, even if nitrogen was flushed
into the kneader [166].
The purity of the polymer affects the melt degradation
of PLLA significantly [127]. Melt degradation is retarded
when dissolved PLLA in chloroform was precipitated in
nonsolvents such as methanol and n-hexane. This proce-
dure removes the non-bonded tin(catalyst) and low-molar
mass impurities, as shown in Table 12. Acid extraction of
the dissolved PLLA was also found to remove a part of the
bonded tin, which resulted in further reduction of the melt
degradation [166].
Addition of tert-butyl peroxybenzoate to the PLLA dras-
tically retards the melt viscosity. The melt viscosity is only
slightly retarded with addition of the same amount of per-
oxides to the purified PLLA—which confirms that the main
effect of peroxides in the PLLA melt is the deactivation of a
tin compound [166].
6.5.2. Degradation by radiation
The molecular weight decreases rapidly with increas-
ing radiation dose but the molecular weigh distribution
of the irradiated copolymer does not change significantly
for doses up to 250 kGy, perhaps because of the random-
ized distribution of the monomer units in the copolymer
[71–73,168]. A drastic decrease in the tensile strength and
substantial embrittlement occur at higher dose levels [73].
Radiation-induced reactions take place mainly in the amor-
phous phase of the polymer; and the degree of crystallinity
of the polymer, which in fact, decides the extent of amor-
phous phase in PLLA, is, therefore, an important parameter.
At lower radiation doses, chain-scission mainly occurs in
the amorphous regions and random chain scission pro-
Mixing temperature (◦ C) kD (×10−4 s−1 )
187.1 ± 3.0 2.28
185.4 ± 2.6 0.59
190.1 ± 4.2 0.97
186.9 ± 1.8 1.03
187.8 ± 3.2 0.84
188.3 ± 2.8 0.71
112 T. Maharana et al. / Progress in Polymer Science 34 (2009) 99–124

ceeds further into crystalline regions at higher doses. The Table 13

PLLA samples irradiated at 30–100 kGy showed a marked
depression in mechanical properties due to the oxidative
chain-scissions in amorphous regions. Gupta et al. [72]
studied the effect of ␥-irradiation on PLA, synthesized by
the solution polymerization of lactic acid under air and N2 .
The presence of air causes a decrease in both chain scission
and cross-linking. The melting temperature decreases with
␥-irradiation dose.
6.5.3. Biodegradation
Biodegradation is influenced by solid-state morphol-
ogy, degree of crystallinity, primary chemical structure,
such as the presence of functional groups and the
hydrophilicity–hydrophobicity balance of PLA [169]. The
degree of crystallinity is the major rate-determining fac-
tor for biodegradation of solid polymers [13]. Consequently,
while attempting to investigate the effects of chemical
structure on biodegradation, it is an important require-
ment that the degree of crystallinity of the various samples
should be almost equal, otherwise, incorrect conclusions
might be drawn as to the identity of the dominant factor
that affects the rate of biodegradation of solid polymers
[13]. In general, chain scission of the PLA main chain takes
place where ester bonds are located, leading to formation of
oligomers. Thus, the number of oligomers after chain scis-
sion will depend upon the number of ester bonds present
in the PLA main chain.
Normally, biodegradation occurs in three steps. In the
first step, depolymerization occurs; and then the depoly-
merized PLA produces lactic acid in the second step. Finally,
in the third step, the lactic acid is consumed in the cit-
ric acid cycle wherein it breaks down to CO2 and H2 O
in the presence of an enzyme produced by microorgan-
isms. Biodegradation of PLA occurs in two ways: namely,
enzymatic degradation, and non-enzymatic degradation,
which include chemical methods such as pH degrada-
tion. Research on the structure and function of degrading
enzymes is advancing rapidly.
The principal mode of degradation for lactic acid-based
homopolymer and copolymer is hydrolysis [121,167] which
takes place in three important steps:
1. Degradation proceeding by diffusion of water into the
material (initially into the more amorphous zones) fol-
lowed by random hydrolysis.
Characteristics of the poly(l-lactide) specimens (0.1 × 5 × 30 mm3 ) [14].
MW (GPC)a (Da) Tm (DSC)b (◦ C) Crystallinity Spherulite
(DSC) (Xc %)c diameter (␮m)
300,000 179.6 30 30
450,000 180.2 15 20
650,000 177.6 5 10
≈3,000,000 177.8 3 10
a
MW: molecular weight; GPC: gel permeation chromatography.
b
Tm : melting temperature at the second heating; DSC: differential scan-
ning calorimetry.
c
Xc (%) = 100 × (Hm − Hc )/H100% .
2. Fragmentation of the material to OLLA.
3. Finally, through a more extensive hydrolysis accompa-
nied by phagocytosis, diffusion and metabolism.
The extent of hydrolysis depends on the size,
hydrophilicity of the given polymer implant, crystallinity
of the polymer and environmental factors such as pH
and temperature [170]. Usually, the degradation time
is shorter for low-molecular-weight-, more-hydrophilic
and more-amorphous polymers. Polymers can often be
tailored to meet specific degradation time through copoly-
merization, molecular weight and end-group selection.
Once the polymer is hydrolyzed, the products of hydrolysis
are either metabolized or excreted.
Degradation is a function of (polymer structure, solu-
tion pH and temperature. Investigations have been carried
out on film samples of PLA having characteristics given in
Table 13 [14]. DSC analysis revealed that the crystallinity
of PLLA increased with degradation time, as shown in
Table 14. PLLA undergoes enzymatic and non-enzymatic
hydrolysis when exposed to aqueous environments, result-
ing in mass loss through heterogeneous bulk degradation
without generation of harmful byproducts. After hydrolytic
degradation, molecular weight of the resulting particles
decreases and crystallinity increases.
Enzymes such as lipases and PHA depolymerases cleave
the ester bond of aliphatic polyesters including PLA. The
hydrophobic domains of enzymes adhere to solid sub-
strates by hydrophobic interactions before hydrolysis by
catalytic domains. The activity of enzymes like lipases is
strongly dependent on the microorganism source, probably
for the reason that the sequence structure of a bind-
ing domain is different, while enzymes have a common

Table 14
Thermal properties of poly(l-lactide) films aged in 0.01 N NaOH (by DSC) [14].

Degradation time (days) A1 A4

Tg (◦ C) Hr (J g−1 ) Tc (◦ C) Tm (◦ C) Xc (%) Tg (◦ C) Hr (J g−1 ) Tc (◦ C) Tm (◦ C) Xc (%)

0 55 – 98.5 179.6 30 60 – 98.4 177.8 3

4 63 4.68 99.1 178.6 33 67 7.78 98.6 177.8 16
42 69 4.89 99.3 178.3 45 71 8.20 98.5 178.4 22
60 70 2.16 – 177.7 46 76 1.5 – 177.7 30
140 72 2.10 – 177.8 47 75.5 3.57 – 177.6 36
175 72 0.94 – 178.0 49 76 2.32 – 177.7 47

A1 = 300,000 Da; A4 = ∼3,000,000 Da.

Tg , Tc and Tm : glass transition, crystallization and melting temperatures, respectively.
Xc (%) = 100 × (Hm − Hc )/H100% .
Hr : excess enthalpy relaxation.
 T. Maharana et al. / Progress in Polymer Science 34 (2009) 99–124
amino acid sequence around the active center regardless
of microorganism species [13].
The rate of enzymatic degradation decreases with
increase in crystallinity. In larger size devices of PLA, the
rate of hydrolytic degradation is higher inside than at the
surface of the material because of the autocatalytic effects
of the carboxylic acid groups trapped inside the device
[5,156,171,172]. The rate of this hydrolytic degradation is
primarily dependent on temperature and humidity. The
intrinsic viscosities of all polymers decrease continuously
when exposed to phosphate buffered saline and a very
sharp mass loss occurs [173]. Pranamuda et al. [10] showed
that out of 25 strains of the genus Amycolatopsis, 15 formed
clear zones on agar plates emulsified with PLA, suggest-
ing a large distribution of PLA degraders within this genus.
The clear zones were also observed with other polyesters
and silk fibroin plates. In liquid cultures of PLA degraders,
there were strains with and without the ability to assimilate
degradation products like LLA.
There are two approaches for gaining further insights
into environmental microorganisms which could degrade
a plastic polymer. The first is to screen and isolate microor-
ganisms degrading the polymer, followed by identification
of their phylogenetic affiliation. The second is to exam-
ine the ability of a given type of strain to degrade the
polymer. A few reports have been published on microbial
degradation of PLA. Torres et al. [16] reported that fun-
gal strains can utilize lactic acid and oligomers generated
from degradation of PLA through abiotic degradation but
were unable to degrade PLA. Ikura et al. [174] reported
isolation of a PLA degrading actinomycete which was tax-
onomically similar to the Amycolatopsis strain. An isolated
strain of Amycolatopsis used in degradation was confirmed
to form a clear zone on a PLA plate [175]. The main degra-
dation mechanism of PLA is hydrolysis of the hydrolysable
Fig. 8. Hydrolysis of PLA [113].
113
ester linkages under different conditions of pH, enzyme and
temperature.
6.5.3.1. Biodegradation mechanism. During the first stage
of degradation, the molecular weight decreases rapidly
with little weight loss. By contrast, in the second stage, the
decrease in molecular weight slows and severe weight loss
as well as initiation of monomer formation is observed.
During the third and final stage, when total weight loss
is experienced, about 50% of the polymer is converted
to monomer. The hydrolysis of the soluble oligomers
continues further, until all are converted to lactic acid
[176]. Recently, a number of published reports have
provided strong evidence that the degradation kinetics
cannot only be described by random chain scissions, but
the role of the end groups as an important contributor
cannot be ignored [177]. For example, the phenomenon
of auto-catalysis by the carboxylic chain ends that are
formed during degradation of PLA is well documented
[156]. Shih [178,179] suggested that chain-end scission is
faster than random chain scission in acidic conditions. An
unambiguous mechanistic explanation, however, cannot
be given for this phenomenon, since the rate constants are
influenced by many factors, including water accessibility,
molecular mobility, local dielectric constant, local pH, etc.
It can be anticipated that the local environment of the chain
ends is much different from that of the bulk chains in the
solid state [180]. Obviously, the contribution of chain-end
scission increases with decreasing molecular weight of the
polymer, since the fraction of chain ends increases as a con-
sequence of the degradation process. In recent applications,
low molecular weight PLA is used instead of relatively high
molecular weight polymer. For example, these are used as
degradable crosslinks in hydrogels, as tablet coating and as
drug release agents [181–187]. Moreover, oligomers of lac-
114 T. Maharana et al. / Progress in Polymer Science 34 (2009) 99–124
tic acid are water-soluble to some extent, which is expected
to have a dramatic influence on the degradation kinetics,
as compared to solid polymers. The degradation rate, of
water-soluble OLLAs (degree of polymerization <10), has
been studied by capillary electrophoresis [188], which
indicated the preferential formation of lactoyllactate,
subsequently degrading slowly to lactic acid. However, a
detailed kinetic and mechanistic analysis of the hydrolysis
process of lactic acid oligomers has not been reported so far.
As illustrated in Fig. 8, cleavage of the ester linkages
by absorption of water produces a successive reduction in
molecular weight. PLA undergoes fragmentation and then
biodegradation when hydrolyzed, and finally produces H2 O
and CO2 as end products. Thus by measuring the amount of
CO2 evolved one can calculate the percentage of biodegra-
dation. In the initial stage, no microorganism is involved
in the degradation but as PLA is fragmented to about
10,000 Da, soil microorganisms can digest the fragments,
producing CO2 and H2 O as shown in Eq. (4)
H2 O
PLA of high MW−→PLA of low MW of about 10, 000
H2 O
−→Lactic acid → CO2 + H2 O (4)
A new PLA-degrading actinomycete, Kibdelosporangium
aridum, degraded more than 97 mg out of 100 mg high
molecular weight (Mn = 3.4 × 105 ) PLA film within 14 days
in liquid culture. l-Lactic acid, the monomeric degradation
product of PLA, was totally assimilated by the actinomycete
[189].
6.5.3.2. Enzymatic degradation. Enzymatic degradation
proceeds only on the surface of a solid substrate both by
surface erosion and weight loss, because enzymes cannot
penetrate solid polymer substrate. The enzymes degrade
selectively amorphous or less ordered regions which allow
enzymes to diffuse into the substrate and subsequently
the crystalline regions are also eventually degraded. In
this process, the molecular weight and molecular weight
distribution of undegraded solid substrate do not change
during the enzymatic degradation because only the poly-
mer on the surface of substrate is degraded and the low
molecular weight degradation products are removed from
the substrate by solubilization in the surrounding aqueous
medium. There are two types of degradation process
based on the point of cleavage. Cleavage can occur either
at random points along the polymer chain (endo-type
degradation) or at the ends of the polymer chain (exo-type
degradation). The degradation processes of lipases or
PHA depolymerases are primarily based on the endo-type
scissions, and thus are not dependent on the molecular
weight and molecular weight distribution [57,180].
6.5.3.3. Non-enzymatic degradation. Degradation due to a
change of pH of the medium [180] is one type of non-
enzymatic degradation. Small amounts of non-enzymatic
catalysts and reagents can diffuse into polymer systems and
cause in-depth degradation. Crystallinity, crosslinking and
other morphological properties of polymers affect the dif-
fusion of catalysts into the system. The shape of the mass
loss vs. time curve supports the occurrence of a hetero-
geneous bulk degradation process [15]. After hydrolytic
degradation the residual particles showed a molecular
weight decrease and a crystallinity increase. It is inter-
esting to note that non-enzymatic degradation proceeds
by an apparently inert first stage of degradation without
weight loss but it results in random cleavage of polymer
chain backbone (endo-type degradation) with a concomi-
tant substantial decrease in molecular weight, leading to a
decrease in mechanical properties such as tensile strength,
ultimate elongation and impact strength [15].
Depending on the above discussions and cited literature,
Table 15 shows effects of various parameters on properties
of PLA. 13 C NMR spectra show that PLA is composed of l
and d lactic acid units. The amount of d-lactic acid in PLLA
is 13–16%. The mechanical and thermal properties of PLLA
become constant when its MW is above a threshold MW of
70,000 Da [119].
7. Melt–solid polycondensation
Synthesis, properties and degradation behavior of PLA
have been discussed above. Criteria leading to synthesis,
selection of catalyst, and effect of operating parameters on
MW of the product are discussed in succeeding sections.
The kinetics and mechanism involved in the different steps
leading to the synthesis of the polymer are also discussed.
The mathematical relationships between parameters of
synthesis and MW are presented.
Melt–solid polycondensation is an approach to increase
the molecular weight of PLLA by increasing the degree of
polymerization. A few investigators [2,3,5,7,9] have worked
on sequential melt–solid polycondensation of LA. Xu et
al. [7] studied the effect of crystallization time of PLLA
pre-polymer on the molecular weight of PLLA. They first
prepared PLLA pre-polymer with a molecular weight of
18,000 by the ordinary melt polycondensation process.
The prepolymer was then crystallized at 105 ◦ C for differ-
ent time periods, and then heated at 135 ◦ C for 15–50 h
for further solid-state polycondensation (SSP). Differential
scanning calorimetry (DSC) and viscosity measurements
were used to characterize the crystalline properties and
molecular weight of the resulting PLLA polymers. The
results showed that the molecular weight reached a maxi-
mum value for a crystallization period of 30 min and SSP of
35 h.
7.1. Key steps leading to PLA synthesis
The polycondensation of LA takes place in several steps
as discussed below. The associated mechanism for each
step is also discussed.
7.1.1. Dehydration
Commercial grade LA, used for PLA synthesis by poly-
condensation reaction, contains about 80–95 wt% LLA
along with 10–15% water, DLA and other impurities. Dur-
ing PC water is also produced and thus, for the forward
reaction to proceed, the water molecules must be removed
from the reaction product mixture as quickly as possible.
This necessitates the removal of water from the raw mate-
rial, LA, before the commencement of the reaction and is
 T. Maharana et al. / Progress in Polymer Science 34 (2009) 99–124 115

carried out during the dehydration step. This includes heat-

Hydro- Thermal Radia-

tion
Degradation properties ing LA under nitrogen at a temperature from 100 to 150 ◦ C

↑
↑
under a pressure of 1000–2000 Pa to reduce the residual
water content to 1–2% [44,82]. If the dehydration step is car-
ried out under continuous flow of N2 gas, removal of water
↓

↑
↑
↓: decreasing trend; ↑: increasing trend; ↑↓: Both increasing and decreasing trends; 0: Unchanged. ↑↓: Both increase and decrease can occur depending on the nature of the factor affecting the said property.
vapor will be comparatively more rapid by helping to drive
lytic

out water molecules. The complete dehydration process is

↑↓

↑↓

↑
↑
carried out in a series of steps involving different tempera-
resistivity

tures, pressures and dehydration time periods [1–3,44,50].

Dielectric Dielectric Volume

For example, LLA is first heated at constant temperature of

ca. 150 ◦ C at atmospheric pressure for 2 h; then the pressure
↑

is reduced to 100 mm Hg(abs) and heating is continued for

Electrical properties

another 2 h at the same temperature; and finally the pres-

constant loss

sure is reduced to 30 mm Hg(abs) and the sample is heated

↓

again for another 4 h without changing the temperature

[1–3,50]. Dehydration is done in stepwise manner to expel
water in a controlled way. However, single-step dehydra-
↑

tion is not uncommon. Chen et al. [44] carried out one-step

strength

dehydration at 100 ◦ C for 1 h at 760 mm Hg(abs). During

Melt

dehydration, oligo(l-lactic acid) (OLLA) is obtained with a

↑

↑
↑
↑
↑

degree of polymerization (DP) varying from 8 to several

Elonga-

hundred.
tion

↑↓

↑↓

↑↓

↑↓
↑

↑
↑

7.1.2. Esterification
modulus
Young’s

In this step, LA is converted into PLLA along with the for-

↑↓

mation of water molecules as a byproduct. As the reaction

↓

product contains water it is imperative that the cata-

modulus
Flexural

lyst should be water–tolerant to get a better yield and

high molecular weight. Some investigators [5,44,190] have
↑

employed water tolerant catalysts so that the degree of

strength modulus strength
Impact

polymerization is not affected. Appropriately substituted

distannoxane catalysts are found to be hydrophobic due to
Mechanical properties

the presence of bulky alkyl groups around the tin atoms

Tensile Tensile

and, therefore, can act as water-tolerant catalysts [44]. The

esterification reaction is generally carried out at 180 ◦ C
↑↓
↑

↑
↓
↓

under a pressure of 30 mm Hg(abs). Higher temperature

increases the vapor pressure of water and helps water
↑↓

↑↓

↑
↓
↓

molecules to escape from the polymer melt and thereby

enhances the rate of the forward reaction. The reduction of
Visco- Solubi- Density % Crystalli-

pressure also helps the water removal process.

nity

↑↓

↑↓

↑
↓

7.1.3. Decompression
This step appears to be trivial but experimentation
↑↓

shows that it helps in achieving high molecular weight

Physical properties

PLLA. Little information is available on the suitability of this

step. The decompression time may range from 3 to 7 h in
Effect of various parameters on the properties of PLA.

lity

↑↓

↑↓

↑↓
↓

which pressure decreases from 30 to 1 mm Hg. It appears

that the decompression step also removes water formed
sity

↑↓

↑↓
↑

during polycondensation and thereby enhances the rate of

reaction. In fact, decompression can increase the molecu-
↑↓

↑↓

↑↓
Tm Tg Hm Cp Tc

lar weight from 3 × 104 to 13 × 104 Da in the case of a TNBT

Thermal properties

↑↓

↑↓

catalyzed PC reaction [44].

↓
↑↓ ↑↓

↑↓

↑↓ ↑↓

↑↓

7.1.4. Melt polycondensation

↓ ↓
↑↓

The polycondensation of LA depends on two thermo-

↓
↓

dynamic equilibria: the dehydration/hydration equilibrium

↑↓

↑↓

Cross-linkers ↑↓
% Crystallinity ↓
Ratio of stereo ↓

↓
↓
Structural property

for ester formation and ring/chain equilibrium for depoly-

comonomer

dimension
Presence of

merization to lactide formation. Melt polycondensation is

Amount of

Melt chain

Plasticizer
Molecular

isomers

Peroxides
Radiation
Stabilizer
weight

carried out above Tm of PLLA, as at this temperature the

Additives
Table 15

d-LA

lactide formed is evaporated to produce a high yield of

polymer [3]. Racemization is also induced during poly-
116 T. Maharana et al. / Progress in Polymer Science 34 (2009) 99–124
condensation [119] and is, most likely, due to the ester
interchange reaction between the polymer chains [190].
There are two ways, in which, the ester linkages between
successive lactic acid units can cleave and reform. One is
acyl oxygen cleavage that does not involve the chiral car-
bon of the lactyl unit. The other is alkyl oxygen cleavage
in which the covalent bond between the oxygen and the
chiral carbon breaks and subsequently reforms resulting in
an inversion of configuration. The change from the l-form
to d,l-form in the presence of the TNBT catalyst is due to
the racemization reaction, which has been confirmed from
analysis of DSC and XRD results [191]. The strong proton
acid co-catalyst promotes the breaking of the ester bond
through the typical carbonyl-oxygen bond cleavage. As the
reaction temperature increases, the probability of alkyl-
oxygen cleavage increases and results in the formation of
an inverted configuration [14,44]. Chen et al. [44] proposed
that the polymerization temperature should be as high as
180 ◦ C to produce high molecular weight PLLA.
7.1.5. Heat treatment
Heat treatment is done around the crystallization tem-
perature (Tc ) of PLLA. In this step the PLLA, which is in
the form of white solid polycondensate, is crushed into
granules and is put into a test tube which is then heated
in vacuum at ca. 105 ◦ C for 1–2 h. Since the crystallization
exotherm is known to extend from 100 to 107 ◦ C, the melt
polycondensate is heat treated at 105 ◦ C to crystallize the
PLLA. It has been reported that the extent of crystallinity is
29 and 30% after 1 and 2 h, respectively. The product, after
heat treatment, becomes resistant to fusion, even when
heated at a higher temperature. Further, it did not reveal
a crystallization exotherm in the DSC curve, which showed
only a melting endotherm at 158 ◦ C. In the process of crys-
tallization, both monomer and catalyst are segregated in
the amorphous region of PLLA. This helps the polymeriza-
tion reaction to take place, even in the solid state, to allow
the yield to reach 100%. Moon et al. [3] reported that during
heat treatment, the MW of PLLA increased from 1.3 × 104 Da
to 1.5 × 104 Da.
7.1.6. Solid-state polycondensation
Although the reaction rate is usually slow in solid-
state reactions, increase in crystallinity does not hinder
the dehydration reaction significantly. This is attributed
not only to the high activity of binary catalyst, even at
low temperature, but also to the high mobility of the PLLA
chains in the amorphous phase [3]. SSP is generally car-
ried out above Tg to enhance the molecular translational
mobility within the amorphous regions of semicrystalline
polymers, while the crystalline regions retain the geomet-
rical shape of the polymer during polymerization [192].
Although the structure of the catalytic site is still unknown,
the polymer terminals extended from the existing crystal
surfaces can be brought sufficiently close to other crystal
end groups present in the amorphous region to assist the
process of esterification and thereby facilitate the growth
of crystals. The polymer chains, thus elongated, can par-
ticipate in the process of crystallization over the crystal
surface available at crystal–amorphous borders, as shown
in Fig. 9. The polymer chains held inside the crystals expe-
Fig. 9. Plausible mechanism of solid-state post-polycondensation of PLA
catalyzed by binary catalyst [3].
rience difficulty in reacting with the neighboring chains
and thus remain as relatively low molecular weight poly-
mer, as can be verified from the bi-modal GPC curves.
The increase in crystallinity can continue until the crys-
tallinity exceeds 43–45%. The crystal growth during the
post-polymerization is very large in the monomer-free
products, and the remaining monomer ratio decreases with
increasing crystal growth [80]. At this stage, the ester-
forming rate among polymer terminals becomes too slow
and the intramolecular ester exchange reaction may over-
come the chain extension to form cyclics together with
the linear fragments. The above supposition can be rea-
sonably supported by the observed decrease in molecular
weight and crystallinity of the polycondensate obtained
after heating for more than 30 h. The bimodal GPC curve
obtained after solid-state polycondensation suggests that
the chain elongation had proceeded in a heterogeneous
manner during the crystallization of the polymer. If a
high vacuum environment is created for an SSP process,
subsequent return to atmospheric pressure may result in
oxidation and discoloration of the polymer [79]. A number
of patents [82,83] are available in which investigators have
used molecular sieves to adsorb water during solid-state
polycondensation. Molecular sieves can be represented by a
chemical formula [M(I),M(II)]O·Al2 O3 ·nSiO2 ·mH2 O, where,
M(I) and M(II) are respectively monovalent (Na and K) and
bivalent (Ca, Sr and Ba) and the range of values for n and m
are 2–10 and 0–9, respectively.
It is reported that in moving from the melt PC step to
the heat treatment step MW increases by 1.5 times and
again increases by 44.7 times in proceeding from the heat
treatment step to the SSP step [3]. The experimental condi-
tions employed by different investigators are summarized
and analyzed in Table 16. On the basis of the information
in Table 16 the following experimental conditions can be
selected for melt–solid polycondensation.
Table 16
In depth analysis of different stages of melt/solid polymerization of LA and their contribution towards molecular weight (MW).

State(S) Pressure (mm Hg) Temperature Steps of polymerization Time range Optimum Enhancement Remarks
and atmosphere (◦ C) reaction (h) time (h) factor for MW

Liquid 760 N2 100 Dehydration 1 1 1. LA is dehydrated under N2 atmosphere in to Oligo(l-LA) (OLLA) whose
degree of polymerization (DP) is 8 to few hundreds
2. In this step excess water in LA gets vaporized

Melt 760 N2 180 Esterification 3–7 7 4 [44] 1. In this step, water is produced and thus water tolerant catalyst is required to
enhance the reaction
2. This step controls the MW
3. Higher time gives higher MW

1–760 N2 180 Decompression 3–7 7 4.3 [44] 1. Esterification time and decompression time are very important for
enhancing MW

T. Maharana et al. / Progress in Polymer Science 34 (2009) 99–124

2. High MW of PLLA can be obtained even in the absence of any additional
reaction promoters, if the decompression step and/or the esterification step is
well controlled
3. Water gets evaporated in this step, thus enhancing reaction rate
4. Higher time gives higher MW

1–10 N2 180 Polycondensation 1–50 20, 40 1. The reaction is done at a temperature (Tr ) where Tg < Tr < Tm
2. Long time heating in melt state of PLLA induces lactide formation and
relevant polymer decomposition rather than polycondensation and hence this
time should be optimized
2. Time of polycondensation reaction is important for controlling MW and yield
4. With time it increases and then decreases. But it has less effect on MW than
esterification and decompression time

Solid 0.5 105 Heat treatment 1–2 2 1.15 times [3] 1. This step is done ∼Tc
2. During this preheating the product crystallizes and became resistive to
fusion even when heated at a higher temperature
3. MW increases with increase in heat treatment time from 1 to 2 h
4. It increases yield

0.5 150 Solid state 10–30 20 2.5 times after 2 h 1. MW increases and then decreases with increase in SSP time
post-polycondensation heat treatment [3]
2. SSP is conducted at ∼Tm for different length of time (10–30 h) to obtain high
polymer. An optimum amount of crystallinity is required to prevent
agglomeration of particles in the reactor
3. SSP reaction essentially takes place in the amorphous region of the polymer,
where all the reactive end groups reside
4. SSP has to be performed at a temperature > Tg (to allow mobility of the end
groups to react) and < Tm
5. Since solid state reactions actually start at much lower temperatures,
compared to molten or solution state, the reaction temperature can range from
sufficiently below Tm to just 5–15 ◦ C below Tm
6. SSP reduces discoloration and degradation associated with high
temperature melt polymerization in molten state
7. Almost all catalysts for melt and solution phase polycondensation are
catalysts for SSP
8. Plasticizers can be used with a view to increase the mobility of the end
groups in the amorphous region, consequently increasing the rate of the SSP

117
118 T. Maharana et al. / Progress in Polymer Science 34 (2009) 99–124

Table 17 its its application. Although, some investigators have used

Relationship between Mw of PLA and catalyst used.
metal–salen Schiff base complexes as initiator for ROP
Catalyst Molecular weight of PLA [192,193], no such investigation is reported so far on the
104 105 106 use of these catalysts for polycondensation reactions.
It can be seen from Table 17 that, tin metal, tin(II)
Protonic acids H3 PO4 H2 SO4
Nafion-H MSA p-TSA
halide, tin oxide and Ni(II) produce high molecular weight
PLA. Appropriately substituted distannoxane catalysts are
Metal compounds
themselves hydrophobic because of bulky alkyl groups
Metals Mg Ti Al Zn Sn
Oxides SnIV TiIV ZnII SbII SnII
around the tin atoms and, therefore, can act as water tol-
Halides GeIV ZrIV ZnII SnIV SnII erant catalysts [44]. Tin atoms, which work as catalytic
Organic acid salts CuII AlIII MnII ZnII YII CoII FeII SnII NiII centers, retard hydrolysis of ester linkages to some extent
Others Al(i PrO)3 Ti(acac) [120]. From a study of variation of the substituents (R = n-
Ti(BuO)4 Bu, X = Cl, OH, NCS) on the distannoxane ladder structure,
Binary catalyst SnII –p-TSA
it was concluded that the molecular weights of the synthe-
sized polymers are relatively insensitive to the nature of
MSA: methane sulfonic acid; p-TSA: p-toluene sulfonic acid; acac: acetyl-
the substituents [5].
acetonato anion; Nafion-H: perfluorinated resinsulfonic acid (registered
trademark of the Dupont Company).
7.3. Kinetics and reaction mechanism of sequential
melt–solid polycondensation
7.2. Selection of catalyst
Homopolycondensation of hydroxycarboxylic acids
As PLLA is primarily used for biomedical and food- such as lactic acid is a reversible process, and in order
packaging applications, the catalysts selected for its to prepare a high molar mass polymer the equilibrium
synthesis should be compatible with these applications. constant for condensation KC has to be high enough. The
Many investigators [1–5,119] have studied the effect of polycondensation rate depends on both chemical (chemical
such catalysts for the synthesis of PLA. They have either reaction) and physical processes (heat treatment, crys-
used catalysts prepared from transition metal compounds tallization). The possible rate-determining steps are (i)
or a combination consisting of transition metal compound chemical reaction control (a reversible chemical reaction);
along with protonic acid in the role of a cocatalyst, as listed (ii) interior diffusion control (diffusion of the volatile reac-
in Table 17. Tin compounds [1,4] are found to be effective for tion products in the solid polymer); (iii) surface diffusion
high molecular weight polymers. Inorganic tin compounds control (diffusion of the volatile reaction product from
are less toxic than organotins and tin(IV) compounds are the surface of the polymer to the surrounding inert gas).
less toxic than tin(II) compounds. Thus inorganic tin will Depending on the process and operating variables, the
be a better choice as a catalyst in comparison to organ- rate of SSP is controlled by one or more of these steps, as
otins. Toxicity grew with increasing tin concentrations. depicted in Fig. 10.
Tetraphenyltin [190] is a catalyst approved by FDA and Vouyiouka et al. [79] has also observed that there is
therefore, can be used safely for the synthesis of polymers no universal agreement on the relevant chemical kinetic
targeted for biomedical applications. Very few investiga- expressions for SSP. The kinetic analysis of SSP shows that
tors have studied the effect of binary catalysts [1,49,95]. the rate of monomer consumption is inversely proportional
Their investigations shows that stannous octanoate is one to the square of the amorphous ratio of PLA, defined as
of the most effective catalysts for the production of high the reciprocal of the crystal ratio, or the fraction of the
molecular weight PLA with high yield. However, like many polymer which is crystalline [80]. Shinno et al. [80], how-
other catalysts, it is difficult to remove this catalyst from ever, observed that the molecular weight did not increase
the polymer, which can lead to cytotoxicity and thus lim- with the monomer consumption as various oligomers are

Fig. 10. Synthesis of PLA by melt–solid PC [3].

 T. Maharana et al. / Progress in Polymer Science 34 (2009) 99–124 119

Table 18
Experimental and proposed characteristic MW of poly(l-lactic acid).

Time of the esterification at Duration of the decompression Time of the polymerization Mw (Da)
760 mm Hg (h) from 760 to 1 mm Hg (h) at 1 mm Hg (h)

Experiment by Chen (2006) 3 7 40 1.3 × 105

3 3 40 0.3 × 105
7 3 40 1.2 × 105
3 3 50 0.3 × 105
3 3 20 0.15 × 105

Proposed by MINITAB 3 6.99 49.99 1.35 × 105

7 7 40 2.232 × 105
7 7 50 2.286 × 105

formed in the post-polymerization stage by the ester inter- Table 19

Experimental conditions for melt polycondensation of LLA.
change reaction, in contrast to most observations [3,86].
The plausible mechanism of solid-state polycondensation Parameter Range
of PLLA catalyzed by the binary catalyst can be explained LLA 20–40 g
as shown in Fig. 9. The rate determining factor in SSP is the Catalyst: co-catalyst (equimolar ratio) 0.4–1.0 wt% w.r.t. OLLA
rate of removal of the condensate water. Greater surface ES time 2–8 h
area within the polymerizing solid favors faster evolution DC time 7–11 h
MPC temperature 180–240 ◦ C
of small molecules. The condensate water can be removed
MPC time 10–30 h
from the solid by using static or dynamic vacuum or by
exposure to a stream of inert gas [194].
Table 20
Fixed operating parameters for melt polycondensation.
8. Suggestions
Operating parameter Value

DH temperature 150 ◦ C
Literature review on melt polycondensation and solid-
DH time 2, 2, 4 h
state polycondensation has been carried out with a view to DH pressure 760, 100, 30 mm Hg
analyzing the published data and to configure better oper- ES pressure 30 mm Hg
ating conditions for the polycondensation process with the ES/DC temperature 180 ◦ C
aim of synthesizing high molecular weight PLA with high DC pressure 30–10 mm Hg
MPC pressure 10 mm Hg
yield. Under this backdrop, data published by Chen et al.
[44] was analyzed by using MINITAB software. While trying
to study the main effect plots and the interaction param- time, esterification temperature, esterification pressure,
eters, it was found that the interaction parameters could decompression time, decompression temperature, decom-
not be studied because of insufficient data points. When pression pressure, melt polycondensation time, melt
regression analysis was carried out for molecular weight as polycondensation temperature and melt polycondensation
a function of esterification time (ET), decompression time pressure affect the process of melt polycondensation of PLA
(DCT) and polymerization time (PT), it provided the follow- directly or indirectly. However, it is quite cumbersome to
ing correlation: investigate such a large number of factors through exper-
iments. Therefore, on the basis of reviewed literature for
MW = −141,964 + 23, 304 Time(ET) + 25, 804 Time(DCT)
synthesis of PLLA, six most significant parameters (such as
+ 536 Time(PT). (5) amount of LLA, amount of catalyst, MPC temperature, ES,
DC and MPC time) can be selected, keeping the remaining
Through the response surface optimization, an attempt was parameters at fixed values, as shown in Tables 19 and 20.
made to figure out whether higher molecular weight poly- The Taguchi method or central composite design methods
mers, as compared to that obtained by Chen et al. [44], for design of experiment can then be applied to study the
could be generated by altering the operating parameters. effects of listed parameters within the specified range of
The study revealed that it was possible to synthesize a interest for the synthesis of PLLA. This will lead to a better
high MW polymer having a MW of about 2.286 × 105 Da correlation between input and output parameters. Again
within the range of operating parameters studied by Chen
et al. [44], as reported in Table 18. It appears that, they Table 21
would have obtained much higher MW polymer had Operating parameters for heat treatment followed solid-state
they followed the sequential melt–solid polycondensation polycondensation.
method. Thus, from the above studies, it can be suggested, Parameter Range
that melt-polycondensation followed by solid-state poly-
Amount of PLLA 6–10 g
condensation will provide high MW PLA. Particle size 150–180 ␮m
It has also been observed from the literature that HT temperature 100–120 ◦ C
fifteen parameters: the amount of LLA, amount of HT time 1–5 h
catalyst, amount of co-catalyst, dehydration time, dehy- SSP time 10–30 h
SSP temperature 160–200 ◦ C
dration temperature, dehydration pressure, esterification
120 T. Maharana et al. / Progress in Polymer Science 34 (2009) 99–124
for carrying out SSP, we have sorted six parameters of sig-
nificance as shown in Table 21 and fixed HT/SSP pressure
to 0.5 mm Hg.
9. Concluding remarks
After reviewing the various routes for the synthesis of
PLA, it can be concluded that production of high molecu-
lar weight PLA with high yield (comparable to ROP), can
be achieved by adopting the route of sequential melt–solid
polycondensation catalyzed by water tolerant catalysts.
Further, the production cost of PLA will be lower than that
of ROP or solution PC. The suggested route for PLA synthesis
is provided, as a flowchart, in Fig. 11.
The salient conclusions of this review are as follows:
1. Ring opening polymerization, solution polyconden-
sation, melt polycondensation, post-polymerization
methods such as melt modification, radiation induced
cross-linking and solid-state polycondensation are dif-
ferent processes available for the production of PLA. All
of these processes have their relative advantages and
disadvantages. From the analysis, it can be concluded
that high molecular weight PLA can be synthesized by
adopting the process of polycondensation followed by
solid-state polycondensation. In this method, the resid-
ual monomer present in the polymer is substantially
less because, during the solid-state polycondensation
process, the monomer and catalyst are concentrated in
Fig. 11. Schematic representation of PLA synthesis.
the amorphous regions of the polymer; and as a result
almost 100% of the monomer is converted to polymer.
During SSP, crystallization takes place in the amorphous
region of the polymer
2. SSP is a slow process. Its deficiencies can be overcome by
the use of specially designed water adsorbent molecular
sieves, so that rate of SSP is enhanced.
3. Properties of PLA do not differ much when prepared by
different routes. Study of various properties of PLA shows
that it can be an effective polymer for application in var-
ious fields: biomedical, packaging, electrical, etc. Among
all these applications, biomedical applications have been
studied to a great extent while study of other applica-
tions is still in the infant stage. Being a biodegradable and
biocompatible polymer it can protect our environment
without causing pollution.
Acknowledgements
One of the authors Ms. T. Maharana is thankful to AICTE,
India for providing a National Doctoral Fellowship. The
authors are also grateful to Prof. I.K. Varma for valuable
suggestions during the preparation of this review article.
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