Bioresource Technology 101 (2010) 8493–8501

Contents lists available at ScienceDirect

Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Review

An overview of the recent developments in polylactide (PLA) research

K. Madhavan Nampoothiri *,1, Nimisha Rajendran Nair 1, Rojan Pappy John 2
Biotechnology Division, National Institute for Interdisciplinary Science and Technology (NIIST), CSIR, Thiruvananthapuram 695019, India

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

Article history: The concept of biodegradable plastics is of considerable interest with respect to solid waste accumula-
Received 9 March 2010 tion. Greater efforts have been made in developing degradable biological materials without any environ-
Received in revised form 17 May 2010 mental pollution to replace oil-based traditional plastics. Among numerous kinds of degradable
Accepted 25 May 2010
polymers, polylactic acid sometimes called polylactide, an aliphatic polyester and biocompatible thermo-
Available online 13 July 2010
plastic, is currently a most promising and popular material with the brightest development prospect and
was considered as the ‘green’ eco friendly material. Biodegradable plastics like polyglycolic acid, polylac-
Keywords:
tic acid, polycaprolactone, polyhydroxybutyrate, etc. are commercially available for controlled drug
Polylactide
Lactic acid
releases, implantable composites, bone fixation parts, packaging and paper coatings, sustained release
Biopolymer systems for pesticides and fertilizers and compost bags etc. This review will provide information on cur-
Biodegradation rent PLA market, brief account on recent developments in the synthesis of lactic acid (monomer of PLA)
Copolymer through biological route, PLA synthesis, unique material properties of PLA and modification of those by
making copolymers and composites, PLA degradation and its wide spectrum applications.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction polysaccharides (starch, cellulose, lignin, etc.), proteins (gelatine,

A wide variety of petroleum-based synthetic polymers are pro-
duced worldwide to the extent of approximately 140 million tons
per year and remarkable amounts of these polymers are intro-
duced in the ecosystem as industrial waste products (Shah et al.,
2008). Plastics are resistant against microbial attack, since during
their short time of presence in nature, could not design new en-
zyme structures capable of degrading synthetic polymers. As more
and more countries and states follow in banning plastic grocery
bags responsible for so-called ‘‘white pollution” around the world,
bioplastics is poised to play a big role as a viable, biodegradable
replacement. Many polymers that are claimed to be ‘biodegrad-
able’ are in fact ‘bioerodable’, ‘hydrobiodegradable’ or ‘photo-bio-
degradable’. These different polymer classes all come under the
broader category of ‘environmentally degradable polymers’. The
‘biodegradability’ of plastics is dependent on the chemical struc-
ture of the material and on the constitution of the final product,
not just on the raw materials used for its production. Therefore,
biodegradable plastics can be based on natural or synthetic resins.
Natural biodegradable plastics are based primarily on renewable
resources (such as starch) and can be either naturally produced
or synthesised from renewable resources. They are coming under
* Corresponding author. Tel.: +91 471 2515366; fax: +91 471 2491712.
E-mail address: madhavan85@hotmail.com (K. Madhavan Nampoothiri).
1
These authors contributed equally.
2
Present address: Institut national de la recherche scientifique 490, rue de la
Couronne Québec (Qc) G1K 9A9, Canada.
wool, silk, etc.), lipid (fats and oil), polyesters produced by plant
or microorganisms (PHA), polyesters derived from bioderived
monomers (polylactic acid) and miscellaneous polymers like natu-
ral rubbers, composites, etc. Non-renewable synthetic biodegrad-
able plastics are petroleum-based. Many natural biodegradable
plastics are blended with synthetic polymers to produce plastics
which meet the functional requirements. Worldwide production
of high-volume consumer plastics continues to be dominated by
non degradable petroleum-based polymers. However, two factors
have made biodegradable polymers economically attractive such
as environmental and economic concerns associated with waste
disposal and intensifying expenses of petroleum production result-
ing from the diminution of the most easily reachable reserves.
Polyesters play a predominant role as biodegradable plastics
due to their potentially hydrolysable ester bonds. The polyester
family is made of two major groups aliphatic (linear) polyesters
and aromatic (aromatic rings) polyesters. Biodegradable polyesters
which have been developed commercially and are in commercial
development are PHA – polyhydroxyalkanoates, PHH – polyhydr-
oxyhexanoate, PHB – polyhydroxybutyrate, PHV – polyhydroxyval-
erate, PLA – polylactic acid, PCL – polycaprolactone, PBS –
polybutylene succinate, PBSA – polybutylene succinate adipate,
AAC – Aliphatic–Aromatic copolyesters, PET – polyethylene tere-
phthalate, PBAT – polybutylene adipate/terephthalate and PTMAT
– polymethylene adipate/terephthalate.
PLA is a sustainable alternative to petrochemical-derived prod-
ucts, since the lactides from which it is ultimately produced can
be produced on a mass scale by the microbial fermentation of

0960-8524/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2010.05.092
8494 K. Madhavan Nampoothiri et al. / Bioresource Technology 101 (2010) 8493–8501

agricultural by-products mainly the carbohydrate rich substances clude base catalyzed degradation of sugars; oxidation of propylene
(John et al., 2006a). PLA can exist in three stereochemical forms: glycol; reaction of acetaldehyde, carbon monoxide, and water at
poly (L-lactide) (PLLA), poly (D-lactide) (PDLA), and poly (DL-lactide) elevated temperatures and pressures; hydrolysis of chloropropion-
(PDLLA). This review will evaluate the demand, recent develop- ic acid and nitric acid oxidation of propylene. The interest in the
ments and challenges in PLA research. fermentative production of lactic acid has increased due to the
prospects of environmental friendliness and of using renewable re-
sources instead of petrochemicals. Besides high product specificity,
2. PLA market
as it produces a desired optically pure L-(+)- or D-( )-lactic acid,
the biotechnological production of lactic acid offers several advan-
Globally, bioplastics make up nearly 300,000 metric tons of the
tages compared to chemical synthesis like low cost of substrates,
plastics market. Even though it sound like lot, only accounts for
low production temperature, and low energy consumption (John
less than 1% of the 181 million metric tons of synthetic plastics
et al., 2007). Lactic acid bacteria (LAB) and some filamentous fungi
the world produces each year. Nevertheless, the bioplastic market
are the chief microbial sources of lactic acid. The organisms that
is growing by 20–30% each year, but not sufficient to meet every-
predominantly yield the L isomer are Lactobacilli amylophilus, Lacto-
one’s need. In 1954, DuPont patented a high-molecular weight PLA
bacilli bavaricus, Lactobacilli casei, Lactobacilli maltaromicus, and
and since many national and international companies have come
Lactobacilli salivarius. Strains such as Lactobacilli delbrueckii, Lacto-
forward to commercialize PLA. Currently, Nature Works LLC is
bacilli jensenii, or Lactobacilli acidophilus yield the D-isomer or mix-
the leader in lactic polymer technology and markets. Over the past
tures of both.
10 years, this company has done extensive work on the develop-
The carbon source for microbial production of lactic acid can be
ment of lactic acid based products, which are of two types-the
either sugar in pure form such as glucose, sucrose, lactose etc. or
polydilactide-based resins (Nature-Works PLAÒ), used for plastics
sugar-containing materials such as molasses, whey, sugar cane
or packaging applications, and the Ingeo™ polydilactide-based fi-
bagassse and cassava bagassse, starchy materials from potato, tap-
bers that are used in specialty textiles and fiber applications. Nat-
ioca, wheat, barley etc. The economics of production of lactic acid
ure Works LLC has constructed a major lactic acid plant in Blair,
and its derivatives is dependent on many factors of which the cost
NÉE, USA, with a capacity of 300 million pounds per year for the
of raw material is very significant (Nolasco-Hipolito et al., 2002).
production of lactic acid and PLA, and it began operating in late
Different food/agro industrial products or residues form the cheap-
2002 (Wee et al., 2006; John et al., 2007). Later, Nature Works
er alternatives to refined sugars for lactic acid production (John
LLC wholly owned by Cargill Inc., and in 2007 the company started
et al., 2006b). Even solid state fermentation studies using inert agro
a joint venture between Cargill Inc., and Teijin Ltd., PURAC bioma-
residual substrates like sugarcane bagasse is reported for lactic
terials are another great figure in biodegradable polylactate and it
acid production (John et al., 2005). Some agricultural byproducts,
develops, manufactures and markets resorbable polymers (homo
which are potential substrates for lactic acid production are corn
and hetero) and monomers worldwide under the PURASORBÒ
starch, lignocellulose/hemicellulose hydrolyzates, cotton seed
brand name. PURASORB has been used commercially for over
hulls, Jerusalem artichokes, corn cob, corn stalks, beet molasses,
thirty-five years in applications as diverse as resorbable surgical
wheat bran, rye flour, sweet sorghum, sugarcane press mud, cas-
sutures, orthopedic implant devices, cosmetic surgery products
sava, barley starch, cellulose, carrot processing waste, molasses
and drug-delivery systems. Mitsui Toatsu (Japan) developed a
spent wash, corn fiber hydrolyzates, etc. Table 1 shows the micro-
polymer from lactic acid under the brand name LACEA. Similarly,
oraganism used and the yield of lactic acid reported from some of
LACTY, PLA pellet for film and fiber extrusion was commercialized
the agro residual substrates.
by Shimadzu, Japan. Nets and non-woven products used in agricul-
Production and recovery of lactic acid was reviewed elaborately
ture, fishing and medical application developed by LACTRON (Kan-
by Vaidya et al. (2005). Some recent studies demonstrated that
ebo Goshen, Japan). SOLANYL (Rodenburg Biopolymers, Holland)
simultaneous saccharification and fermentation can replace the
produce PLA from potatoes and production capacity was about
classical double step fermentation by the saccharification of star-
40,000 tonnes per year. GALACTIC (Belgium) commercialized PLA
chy or cellulosic biomass and conversion to lactic acid concurrently
pellets for multipurpose like production of film, fibers, etc. Reliance
by adding inoculum along with the substrate degrading enzymes.
Life Sciences has developed a complete process for production of
It not only reduces the cost of production by avoiding high energy
Poly Lactic Acid (PLA) from renewable feedstock by bacterial fer-
consuming biomass saccharification, but also gives higher produc-
mentation. They were also developing co-polymers – (of Lactic
and Glycolic Acid–PolyLactic-co-Glycolic Acid or PLGA)-of varying
ratios and other biodegradable polymers including polyvinylcapro-
Table 1
lactums, polyurethanes for biomedical applications and drug- Starchy and cellulosic materials used for the production of lactic acid. Source: John
delivery systems based on nanotechnology using PLA/PLGA for et al. (2008).
generic drugs as well as therapeutic proteins. Other application
Substrate Microorganism Lactic acid
that is being pursued in Reliance involves preparation of fibers of yield
PLA/PLGA/PGA by wet/melt spinning for sutures, scaffolds, etc.
Wheat and rice bran Lactobacillus sp. 129 g/l
Corn cob Rhizopus sp.MK-96–1196 90 g/l
Pretreated wood Lactobacillus delbrueckii 48–62 g/l
3. Lactic acid-PLA monomer
Cellulose Lactobacillus coryniformis ssp. 0.89 g/g
torquens
Lactic acid (2-hydroxypropionic acid), CH3–CHOHCOOH, is the Barley Lactobacillus caseiNRRLB-441 0.87–0.98 g/g
most widely occurring hydroxycarboxylic acid, having a prime po- Cassava bagasse L. delbrueckii NCIM 2025, L casei 0.9–0.98 g/g
Wheat starch Lactococcus lactis ssp. lactis ATCC 0.77–1 g/g
sition due to its versatile applications in food, pharmaceutical, tex-
19435
tile, leather and chemical industries (Vickroy, 1985). Lactic acid is a Whole wheat Lactococcus lactis and Lactobacillus 0.93–0.95 g/g
naturally occurring organic acid that can be produced by chemical delbrueckii
synthesis or fermentation. Chemical synthesis of lactic acid is Potato starch Rhizopus oryzae, R. arrhizuso 0.87–0.97 g/g
mainly based on the hydrolysis of lactonitrile by strong acids, Corn, rice, wheat Lactobacillus amylovorous ATCC <0.70 g/g
starches 33620
which provide only the racemic mixture of D-and L-lactic acid.
Corn starch L. amylovorous NRRL B-4542 0.935 g/g
Other possible chemical synthesis routes tried for lactic acid in-
 K. Madhavan Nampoothiri et al. / Bioresource Technology 101 (2010) 8493–8501
tivity than the single step conversion by providing the adequate
sugar release (John et al., 2009). Direct conversion of starchy bio-
mass to lactic acid by bacteria possessing both amylolytic and lac-
tic acid producing character will eliminate the two step process to
make it economical (Reddy et al., 2008). John et al. (2008) devel-
oped a low pH tolerant, fast growing mutant of Lactobacillus del-
brueckii by mutagenesis using nitrous acid and genome shuffling
was done between this mutant and an amylase producing non-fas-
tidious Bacillus amyloliquefaciens to get a fusant capable of grow-
ing at low pH and utilizing starchy materials directly for L-lactic
acid production.
In 1990, the worldwide production volume of lactic acid had
grown to approximately 40,000 metric tonnes per year with two sig-
nificant producers, CCA Biochem in The Netherlands, with subsidiar-
ies in Brazil and Spain, and Sterling Chemicals in Texas City, TX, USA,
as the primary manufacturers and from Asia, Musashino in Japan.
CCA uses carbohydrate feedstocks and fermentation technology,
while Sterling and Musashino use a chemical technology. The major
manufacturers of fermentative lactic acid include Natureworks LLC,
Purac (Netherlands), Galactic (Belgium), Cargill (USA), and several
Chinese companies (Wee et al., 2006).
4. Polymerization
The existence of both a hydroxyl and a carboxyl group in lactic
acid enables it to be converted directly into polyester via a polycon-
densation reaction. However, the conventional condensation poly-
merization of lactic acid does not increase the molecular weight
sufficiently unless organic solvents are used for azeotropic distilla-
tion of condensation water and the polymerization time is very long.
Addition of acidic catalysts, such as boric or sulfuric acid accelerates
the esterification and transesterification processes, but also cata-
lyzes side reactions at temperatures above 120 °C. Therefore, poly-
condensation of aqueous DL-lactic acid never gave Mn’s above 3000,
as against Mn’s up to 6500 reported for pure L-lactide. When the pre-
condensates obtained by dehydratization up to 120 °C are heated to
180 °C in the presence of nonacidic transesterification catalysts,
such as PbO, a moderate yield of relatively high-molecular weight
PLA may result (Schneider and Wilmington, 1955).
The most common way to obtain high-molecular-weight poly
lactic acid is through ring-opening polymerization of lactide. The
intermediate lactide, a cyclic lactic acid dimer, is formed in the first
step when the condensation product water is removed by evapora-
tion during oligomerization. L-lactic acid, D-lactic acid or mixtures
Fig. 1. Stereoforms of lactides.
8495
thereof can be polymerized to corresponding low-molecular-
weight poly (lactic acid) oligomer, which is in then catalytically
depolymerized through an internal transesterification, i.e., by
‘back-biting’ reaction to lactide. Three stereoforms of lactide are
possible: L-lactide, D-lactide, and meso-lactide (Fig. 1). In the sec-
ond step, purified L-lactide, D-lactide, DL-lactide (50:50 mixture of
L and D isomers), or meso-lactide monomer is converted into the
corresponding high-molecular weight polyester by catalytic ring-
opening polymerization. Ring-opening polymerization was carried
out most commonly by a stannous octoate catalyst, but for labora-
tory demonstrations tin (II) chloride is often employed. Stannous
alkoxide, a reaction product between stannous octoate and alcohol,
was proposed as the substance initiating the polymerization
through coordinative insertion of lactide. Alcohol could affect the
polymerization through reactions leading to initiator formation,
chain transfer, and transesterification. Carboxylic acids affect the
polymerization through a deactivation reaction. Experiments have
shown that alcohol increases PLA production rate while carboxylic
acid decreases it. The higher the alcohol concentration, the lower is
the polymer molecular weight. However, the final molecular
weight of PLA is not sensitive to the carboxylic acid concentration.
Recently, Gupta and Kumar (2007) made an effort to present an up-
dated review on the various aspects of PLA synthesis. In this re-
view, a collection of more than 100 catalysts for the synthesis of
PLA are mentioned. Table 3 shows some of the catalysts commonly
used for PLA synthesis. As mentioned before, Polymerization of a
racemic mixture of L- and D-lactides usually leads to the synthesis
of poly-DL-lactide (PDLLA) which is not crystalline but amorphous.
Use of stereospecific catalysts can lead to heterotactic PLA which
has been found to show crystallinity. The degree of crystallinity,
and hence many important properties, is controlled by the ratio
of D to L enantiomers used. The ring-opening polymerization of L-
lactide using different organic monocarboxylic iron complexes
has also been reported. It was observed that the acetate anion as
well as the iron partly, are chemically attached to the polymer
chain, and the proposed polymerization mechanism is an anionic
type of coordination insertion.
Cargill Dow LLC has developed a patented, low-cost continuous
process for the production of lactic acid based polymers (Gruber
et al., 1992, 1993, 1994). The process combines the substantial
environmental and economic benefits of synthesizing both lactide
and PLA in the melt rather than in solution and, for the first time,
provides a commercially viable biodegradable commodity polymer
made from renewable resources. The process starts with a contin-
8496 K. Madhavan Nampoothiri et al. / Bioresource Technology 101 (2010) 8493–8501

Table 2 5. Material properties

Material properties of PLA.

Nature works PLA Biomer L9000 Poly (lactic acid) exists as a polymeric helix, with an ortho-
Physical properties rhombic unit cell. Properties of PLA depend on the component iso-
Melt flow rate (g/10 min) 4.3–2.4 3–6 mers, processing temperature, annealing time and molecular
Density (g/cm3) 1.25 1.25 weight. Poly-L-lactide (PLLA) is the product resulting from poly-
Haze 2.2
merization of L-lactide. PLLA has a crystallinity of around 37%, a
Yellowness index 20–60
glass transition temperature between 50–80 °C and a melting tem-
Mechanical properties
perature between 173–178 °C. Because of the stereo regular chain
Tensile strength at yield (Mpa) 53 70
Elongation at yield (%) 10–100 2.4 microstructure, optically pure polylactides, poly (L-lactide) (PLLA)
Flexular modulus (Mpa) 350–450 3600 and poly (D-lactide) (PDLA), are semi crystalline. The crystallization
Thermal properties ability of polylactides decreases with chain stereoregularity and
HDT (°C) 40–45, 135 below 43% optical purity crystallization is no longer possible
VICAT Softening point (°C) 56 (Sarasua et al., 1998). However, regardless of the different lactyl
GTT (°C) 55–56 structural unit chain arrangement tried for tuning the properties
Melting point 120–1704
of polylactides by diverse polymerization methods, both amor-
phous and crystalline polylactides use to show brittle behavior at
room and body temperatures (Franschini et al., 2005). Crystalliza-
tion of polylactides in the form of stereo complex also leads to a
Table 3
brittle mechanical behavior (Sarasua et al., 1998). Polylactide is a
Different catalysts used for the production of PLA.
clear, colorless thermoplastic when quenched from the melt and
Polymer Catalyst Solvent Molecular is similar in many respects to polystyrene. Polylactic acid can be
weight
processed like most thermoplastics into fiber and film. The melting
D, LPLA/L-PLA Aluminium Toluene Mn. 90,000 temperature of PLLA can be increased 40–50 °C and its heat deflec-
Isopropoxide
tion temperature can be increased from approximately 60–190 °C
D-L PLA Stannous octoate Alcohols Mw < 3,50,000
by physically blending the polymer with PDLA (poly-D-lactide).
L-PLA Stannous octoate Alcohols, Mn, 250,000
PDLA and PLLA form a highly regular stereo complex with in-
carboxylic
acid creased crystallinity. The density of amorphous poly (L-lactic acid)
L-PLA Stannous octoate and compounds Toluene Mn = 40,000– has been reported as 1.248 g ml 1 and for crystalline PLLA as
of titanium and zirconium 100,000 1.290 g ml 1. The density of solid polylactide was reported as
D-PLA Stannous trifluoromethane Ethanol – 1.36 g cm 3 for L-lactide, 1.33 g cm 3 for meso-lactide, 1.36 g cm 3
sulfonate, scandium(III)
L-PLA for crystalline polylactide and 1.25 g cm 3 for amorphous polylac-
trifluoromethane sulfonate
D-L PLA tide. Poly (98% L-lactide) had a density of 1.240–0.002 g cc 1 and
poly (94% L-lactide) had a density of 1.243–0.002 g cc 1 (Auras
et al., 2004). In general, polylactides are soluble in dioxane, aceto-
L-PLA Mg, Al, Zn, Titanium alkoxides Methylene – nitrile, chloroform, methylene chloride, 1,1,2-trichloroethane and
chloride dichloroacetic acid. Ethyl benzene, toluene, acetone and tetrahy-
L-PLA Yttrium tris(2,6-di-tert butyl 2-propanol, Mn < 25,000 drofuran only partly dissolve polylactides when cold, though they
phenolate) (in toluene) butanol,
are readily soluble in these solvents when heated to boiling tem-
ethanol
Zn lactate No solvent Mn = 212,000
peratures. Crystalline poly (L-lactide) is not soluble in acetone,
D-LPLA

Butylmagnesium, Grignard Ethers Mn < 300,000

ethyl acetate or tetrahydrofuran. Poly (lactid acid) is a slower-crys-
D-L PLA
reagent tallizing material, similar to poly (ethylene terephthalate). The
L-PLA

Potassium naphthalenide THF, Mn < 16,000

L-PLA
toluene
L-PLA Complexes of iron with acetic, No solvent
butyric, siobutyric and
dichloroacetic acid
uous condensation reaction of aqueous lactic acid to produce low
molecular weight PLA pre-polymer. Next, the pre-polymer is con-
verted into a mixture of lactide stereoisomers using tin catalysis
to enhance the rate and selectivity of the intramolecular cycliza-
tion reaction. The molten lactide mixture is then purified by vac-
uum distillation. Finally, PLA high molecular-weight polymer is
produced using a tin-catalyzed, ring-opening lactide polymeriza-
tion in the melt, completely eliminating the use of costly and envi-
ronmentally unfriendly solvents. This process is currently in
operation at an 8. 106 lb per year market development facility in
Minnesota.
Jacobsen et al. (2000) developed, based on a new catalytic sys-
tem, a reactive extrusion polymerization process, which can be
used to produce PLA continuously in larger quantities and at lower
costs than before. This extrusion polymerization process has been
developed and tested with laboratory scale machines and the pos-
sibilities to extend this polymerization process to lactide based
block copolymers have been investigated.
fastest rates of crystallization for pure PLA are found in the temper-
ature of 110–1300 °C, which yields spherulitic crystalline morphol-
Mw = 150,000 ogy. Crystalline PLA is soluble in chlorinated solvents and benzene
at elevated temperatures. Poly (lactic acid) can be crystallized by
slow cooling, annealing it above the Tg, or strain crystallized. All
polylactides are insoluble in water, some alcohols and alkanes. Ta-
ble 2 summarizes some of the general properties of PLA. The mate-
rial properties of PLA were reported earlier by Drumright et al.
(2000). Recently, Lim et al. (2008) discussed the specific process
technologies such as extrusion, injection molding, injection stretch
blow molding, casting, blown film, thermoforming, foaming,
blending, fiber spinning, and compounding related to PLA.
6. Copolymers, blends and composites of PLA
To improve the quality and reduce the cost of production, lactic
acid polymerizes with other monomers or PLA blend with other
polymers. Poly (lactic-glycolic acid), a copolymer, have the approval
of FDA for the clinical uses. VIRYL (Ethicon Inc.) is composed of lactic
acid and glycolic acid in 2:23 ratio. The main application of this
copolymer is in controlled drug release. The ester linkages in PLA
are sensitive to both chemical hydrolysis and enzymatic chain cleav-
age. PLA is often blended with starch to increase biodegradability
 K. Madhavan Nampoothiri et al. / Bioresource Technology 101 (2010) 8493–8501
and reduce costs. Starch concentration in PLA–starch blend is a key
parameter determines mechanical properties of blend. Tensile
strength and elongation decreases as starch concentration increases.
Starch is a hydrophilic polymer and sensitive to water and PLA is
hydrophobic and water resistant. Water absorption increases as
the starch concentration increases. However, the brittleness of the
starch-PLA blend is a major drawback in many applications. To rem-
edy this limitation, a number of low molecular weight plasticisers
such as glycerol, sorbitol and triethyl citrate are used. Blends of
PLA and starch (10–20%) have been commercialized as Novon (Eco-
star, Germany). One type PLA can be form miscible blend with other
isomer PLA and with other various polymers, such as Poly ethylene
oxide (Nijenhuis et al., 1996), polyvinyl acetate (Gajria et al.,
1996), polyethylene glycol (Sheth et al., 1997). As PLA remains rela-
tively costly, it is used as a matrix in biocomposites combined with
natural fibers. With Jute-PLA composite tensile strength and tensile
modulus increased with a slight reduction in the elongation at max-
ium stress compared with PLA.
The high crystallinity of the polymer (PLA) interferes with con-
trolled degradation, reducing compatibility with soft tissues and
presenting an obstacle to application as biodegradable soft plastics.
Many approaches to overcome these problems in PLLA, for exam-
ple, stereocopolymer according to enantiomeric composition, block
copolymerization with other polyethers, branched PLLA or blend
with other polymers were carried out to control the degradation
rate by varying the crystallinity (Tsuji and Ikada, 1992; Martin
and Averous, 2001).
Ohya et al. (1998) reported a method to achieve graft-polymer-
ization of LA on polysaccharides using trimethylsilyl (TMS)-pro-
tected polysaccharides. By introducing TMS protecting groups
with chlorotrimethylsilane/pyridine, low-molecular-weight poly-
saccharides become soluble in organic solvents and the number
of initiating groups (i.e., the number of graft chains) can be con-
trolled. Polylactide (PLA)-grafted polysaccharides with various
lengths and numbers of graft chains were synthesized using a tri-
methylsilyl protection method. The graft-copolymer films exhib-
ited a lower glass transition temperature (Tg); melting
temperature, crystallinity, and higher viscosity properties com-
pared to PLA films. Moreover, the usefulness of graft-copolymer
as a plasticizer was investigated with1: 4 blend films prepared
from the graft-copolymers and PLA. The blend films showed lower
Tg and crystallinity, and higher viscosity properties compared to
PLA films (Ouchi et al., 2003).
Varying types of chemicals, such as citrate esters, have been
tried to plasticize PLA (Martin and Averous, 2001). Recently, plast-
icizers such as poly (ethylene glycol) (PEG), glucose monoesters
and partial fatty acid esters (Hoffman, 2002) were used to improve
the flexibility and impact resistance of PLA. Calcium phosphate
ceramics such as hydroxyapatite or b-tricalcium phosphate show
high biological compatibility and safety in living tissues, such that,
currently, they are used clinically as biomaterials for bone repair.
These ceramics, however, have disadvantages in that their tough-
ness is not sufficiently high and that their modulus of elasticity
(80–100 GPa) is much higher than that of natural bone. Materials
with a high modulus induce a problem of stress shielding which
leads to bone resorption. Since the stress shielding is apt to occur
due to use of rigid materials such as conventional metals or ceram-
ics, bioresorbable materials with modulus of elasticity that is sim-
ilar to that of natural bone (5–15 GPa) are requisite for some
applications such as bone plates or temporary internal fixation of
bones broken or damaged. Polylactic acid showing bioresorbability
is one of the great potential candidates for the applications. The
resorption rate is controllable by degree of polymerization or copo-
lymerizing. The modulus of elasticity of polylactic acid, however, is
much lower (2–3 GPa) than natural bone. Kasuga et al., 1999 pre-
pared the composite of PLA and b-Ca(PO3)2 fibers for medical appli-
8497
cations. Poly(l-lactic acid)-poly(l-lactic acid-co-citric acid)-
poly(ethylene glycol) multiblock copolymers (PLLA–PLCA–PEG)
were synthesized through polycondensation reaction and the
properties of scaffolds such as swelling and degradation behaviors,
morphology and mechanical moduli were fully investigated (Wang
et al., 2007). The mechanical flexibility improves as the content of
PLLA–PLCA–PEG copolymers in the scaffolds increases. The study
shows that the modification of PLLA scaffold with PLLA–PLCA–
PEG shall broaden its applications in tissue engineering. To use
as starting materials in the medical industry requires a high purity
of all compounds and advanced quality systems. Regulatory as-
pects such as cGMP and Drug or Device Master Files have to be ta-
ken into account when producing polylactides for medical
applications (Bendix, 1998).
It is interesting to note that (Murariu et al., 2008) large amounts
of stable b-anhydrite II (AII), a specific type of dehydrated gypsum
and a by-product of lactic acid production process, can be melt-
blended with bio-sourced and biodegradable polylactide (PLA) to
produce economically interesting novel composites with high ten-
sile strength and thermal stability.
7. Degradation of PLA
Polymer degradation occurs mainly through scission of the
main chains or side chains of macromolecules. In nature, polymer
degradation is induced by thermal activation, hydrolysis, biological
activity (i.e., enzymes), oxidation, photolysis, or radiolysis (Muller,
2008). Because of the coexistence of biotic and nonbiotic processes,
the entire mechanism of polymer degradation could, in many
cases, also be referred to as environmental degradation. A variety
of chemical, physical and biological processes and thus different
degradation mechanisms can be involved with the degradation of
a polymer. Environmental factors not only influence the polymer
to be degraded, they also have a crucial influence on the microbial
population and on the activity of the different microorganisms
themselves. Parameters such as humidity, temperature, pH, salin-
ity, the presence or absence of oxygen and the supply of different
nutrients have important effects on the microbial degradation of
polymers, and so these conditions must be considered when the
biodegradability of plastics is tested. The process is also dependent
upon the chemical and physical characteristics of the polymer.
These include diffusivity, porosity, morphology, cross linking, pur-
ity, chemical reactivity, mechanical strength, thermal tolerance,
and resistance to electromagnetic radiation.
PLA degradation has been found to be dependent on a range of
factors, such as molecular weight, crystallinity, purity, tempera-
ture, pH, presence of terminal carboxyl or hydroxyl groups, water
permeability, and additives acting catalytically that may include
enzymes, bacteria or inorganic fillers (Park and Xanthos, 2009).
Pyrolysis, chemical decomposition of a condensed substance by
heating, is a method of treating polylactide. Copyrolytic techniques
have received much attention in recent years because they provide
an alternative way to dispose and convert waste origins into higher
value fuel and the specific benefits of this method potentially in-
clude: the reduction of the volume of waste; the recovery of chem-
icals and the replacement of fossil fuels. Copyrolysis of PLA and
biomass offers an alternative waste treatment option and may
act as an upgrading step during the pyrolysis of biomass (Gang
and Aimin, 2008). PLA can be hydrolyzed with boiling water or
steam to lactic acid, which can be recycled back to the monomer.
This could lead to molecular recycling and would allow the recy-
cling of both manufacturing plant materials and post consumer
packaging. PLLA could be hydrolyzed at 180 °C to 350 °C for up
to 30 min, obtaining L-lactic acid as the final product (Auras
et al., 2004). De Jong et al. (2001) observed PLA depolymerization
8498 K. Madhavan Nampoothiri et al. / Bioresource Technology 101 (2010) 8493–8501
by a progressive release of dimers in alkaline conditions. The end-
chain degradation may be explained by an intramolecular transe-
sterification. An electrophilic attack, catalyzed by a base, of the hy-
droxyl end-group on the second carbonyl group leads to a ring
formation and the polymer is shortened by the hydrolysis of the
resulting lactide. Next step involves the hydrolysis of the free lac-
tide into two molecules of lactic acid. The intramolecular degrada-
tion occurs by a random alkaline attack on the carbon of the ester
group, followed by the hydrolysis of the ester link. Thus, new mol-
ecules with low molecular weight are produced but in acidic con-
ditions the protonation of the hydroxyl end-group forms an
intramolecular hydrogen bond. The hydrolysis of the ester group
allows the release of a lactic acid molecule leading to the decrease
of the degree of polymerization of the PLA. An intramolecular ran-
dom protonation of carbon of the ester group conduces also to the
hydrolysis of ester linkages and it gives different fragments of low-
er molecular weights (Lucas et al., 2008).
PLA is also said to decompose into carbon dioxide and water in a
‘‘controlled composting environment” in fewer than 90 days. Com-
posting is the accelerated degradation of heterogeneous organic
matter by a mixed microbial population in a moist, warm, aerobic
environment under controlled conditions (Ghorpade et al., 2001).
They demonstrated that PLA could be composted efficiently when
added in small amounts (<30% by weight) to pre-composted yard
waste.
Toshinori et al. (2002) investigated the degradation behaviors of
poly (lactic acid) products used in farming by an evaluation meth-
od under composting. Food residue was used as a composting
material, and test pieces of PLA products were left in composting
reaction. The degradability of PLA was measured directly after col-
lection of the test pieces from a reactor. We found that PLA soft
film samples degraded within 3 weeks and both PLA band samples
and PLA rope samples degraded within 6 weeks. Thus, all the PLA
products rapidly degraded under composting conditions (Toshinori
et al., 2002). Kale et al. (2007), investigated the biodegradation per-
formance of polylactide (PLA) bottles under simulated composting
conditions according to ASTM and ISO standards, and these results
are compared with a novel method of evaluating package biodeg-
radation in real composting conditions. Two simulated composting
methods were used in this study to assess biodegradability of PLA
bottles: (a) a cumulative measurement respirometric (CMR) sys-
tem and (b) a gravimetric measurement respirometric (GMR) sys-
tem. Both CMR and GMR systems showed similar trends of
biodegradation for PLA bottles and at the end of the 58th day the
mineralization was 84.270.9% and 77.8710.4%, respectively.
As far as biodegradability is concerned, it has been confirmed
that PLA is naturally degraded in soil or compost even if it is known
that PLA is less susceptible to degradation than other aliphatic bio-
degradable polymers such as poly(-caprolactone) (PCL) in natural
environment (Ghorpade et al., 2001). It was reported that the prod-
ucts of the PLA hydrolytic degradation can be totally assimilated by
microorganisms such as fungi or bacteria (Tsuji et al., 1998; Li
et al., 2000; Hoshino et al., 2003). Biodegradation of PLA and its
copolymers are usually done by esterases, proteases and lipases se-
creted from microorganisms. Tokiwa and Jarerat (2004) tested the
biodegradability of polylactide by using proteinase K of the mold
Tritirachium album. Oda et al. (2000) tested many commercial pro-
tease enzymes for degradation of PLA. Among them Savinase 16.0L
(Novo Nordisk Bioind. Co., Chiba) from Bacillus lentis and Protin A
(Daiwa Kasei Co., Osaka) from B. subtilis showed higher degrading
activity. Pranamuda et al. (2001) reported the purification of PLA-
degrading enzyme from Amycolatopsis strain-41, with molecular
weight of 43 kDa. The purified enzyme is able to degrade casein,
silk fibroin, succinyl-(L-alanyl-L-alanyl-L-alanine)-pnitroanilide
(Suc-(Ala) 3-pNA), but not PCL nor PHB. Lipase preparations from
porcine pancreas, Candida cylindracea and Rhizopus arrhizus were
able to hydrolyze the amorphous polymer, poly (DL-lactide). Toki-
wa and Jarerat (2004); reported that an actinomycete strain de-
grade PLA which was taxonomically similar to Amycolatopsis. A
silk degrading strain of Amycolatopsis isolated and proved to de-
grade PLA plate (Tokiwa et al., 1999). PLA-degrading actinomycetes
belong phylogenetically to family of Amycolatopsis (Pranamuda
and Tokiwa, 1999), Pseudonocardiaceae, and other related genera,
including Lentzea, Streptoalloteichus, Kibdelosporangium and Sac-
charothrix (Tokiwa and Jarerat, 2004).
Jarerat and Tokiwa (2001, 2003) mentioned that Tritirachium al-
bum is the only reported PLA degrading fungal strain so far. Poly-
mer with low molecular weight is more susceptible than high-
molecular weight one and amorphous can more easily degrade
than crystalline .The low molecular weight oligomers were totally
degraded regardless of their stereo isomeric property by Fusarium
moniliforme and Pseudomonasputida, but couldn’t degrade high
molecular polymeric form (Torres et al., 1996). PLA degradation
rate was greatly increased by adding 0.1% (w/v) gelatin into the ba-
sal medium, indicating that gelatin induces the enzyme capable of
degrading PLA. The reports on PLA film degradation by Saccharo-
thrix waywayandensis (renamed as Lentzea waywayandensis) (Jar-
erat and Tokiwa, 2003) and by Kibdelosporangium aridum (Jarerat
et al., 2003) substantiated that the degradation of PLA is markedly
increased by addition of gelatin into the culture medium. A new
fluorescent assay for the degradation of polylactic acid was devel-
oped based on the reaction of the carboxyl groups of lactic acid and
its soluble polymers with a fluorescent agent, o-phthalaldehyde, in
the presence of 1-ethyl-3-(3dimethylaminopropyl) carbodiimide
(Vichaibun and Chulavatnatol, 2003). The assay was used to show
polylactic acid degradation catalyzed by proteinase K, subtilisin
Carlsberg and subtilisin BPN’. Proteinase K was found to be a good
catalyst for PLA degradation whereas subtilisin Carlsberg and sub-
tilisin BPN’ were not as effective.
The proteolytic degradation was shown to be activated or inhib-
ited by the presence of detergent. Detergents causing activation in-
cluded heptylthioglucoside and octyl-glucoside. Various analytical
techniques such as weighing, SEC, 1H NMR, IR, DSC, X-ray, ESEM
and CZE were successfully used by researchers (Huang et al.,
2004a,b) to monitor property changes during degradation such as
water absorption, weight loss, molecular weight distribution, com-
position, bulk and surface morphologies, thermal behavior, and re-
lease of water-soluble oligomers into the aqueous phase etc.
One of the drawbacks of processing PLA in the molten state is its
tendency to undergo thermal degradation. According to Sodergard
and Stold (2002), thermal degradation of PLA can be due to several
reasons such as (a) hydrolysis by trace amounts of water, (b) zip-
per-like depolymerization, (c) oxidative, random main-chain scis-
sion, (d) intermolecular transesterification to monomer and
oligomeric esters, and (e) intramolecular transesterification result-
ing in formation of monomer and oligomer lactides of low molec-
ular weights. Kopinke et al. (1996) proposed that above 200 °C, PLA
can degrade through intra- and intermolecular ester exchange, cis-
elimination, radical and concerted non-radical reactions, resulting
in the formation of CO, CO2, acetaldehyde and methylketene. Inter-
estingly, McNeill and Leiper (1985) on the other hand proposed
that thermal degradation of PLA is a non-radical, ‘‘backbiting” ester
interchange reaction involving the -OH chain ends.
8. Applications
PLA meets many requirements as a packaging thermoplastic and
is suggested as a commodity resin for general packaging applica-
tions. When plasticized with its own monomers, PLA becomes
increasingly flexible so that a continuous series of products can be
prepared that can mimic PVC, LDPE, LLDPE, PP, and PS. Degradation
 K. Madhavan Nampoothiri et al. / Bioresource Technology 101 (2010) 8493–8501
is increased with increasing plasticizer, and shelf life is favored by
decreasing plasticizer content and/or orientation. Because it is bio-
degradable, it can also be employed in the preparation of bioplastic,
useful for producing loose-fill packaging, compost bags, food pack-
aging, and disposable tableware. In the form of fibers and non-wo-
ven textiles, PLA also has many potential uses, for example as
upholstery, disposable garments, awnings, feminine hygiene prod-
ucts, and nappies. PLA has been used as the hydrophobic block of
amphiphilic synthetic block copolymers used to form the vesicle
membrane of polymersomes. For a few years, natural foods purvey-
ors such as Newman’s Own Organics and Wild Oats have been qui-
etly using some PLA products, but the material got its biggest
boost when Wal-Mart, the world’s largest retailer, announced that
they will sell some produce in PLA containers. As a kind of important
aliphatic polyester, Poly lactic acid (PLA) is biodegradable, and it has
extensive applications in biomedical fields, including suture, bone
fixation material, drug delivery microsphere, and tissue engineering
(Zhao et al., 2004; Mehta et al., 2005). At the same time, as another
kind of important biodegradable material with easily functionalized
structure, poly (phosphate ester) has been extensively applied in
biomedical fields, including drug delivery material also (Narendra
and Kishore, 2002; Zhao et al., 2003; Huang et al., 2004a,b; Li et al.,
2006). A major application field for microspheres is controlled drug
delivery. Typically an active pharmaceutical ingredient such as a
protein or peptide is homogeneously distributed in the matrix of a
biodegradable polymer microsphere. The most commonly used
materials for these systems are polylactide (PLA) and its copolymers
with glycolide (PLGA). The adjuvant effect of biodegradable poly-
(D,L-lactic acid) granules is capable of antigen release following intra-
peritoneal injection.
Poly (esters) based on poly (lactic acid) (PLA), poly-(glycolic
acid) (PGA), and their copolymers, poly (lactic acid-co-glycolic
acid) (PLGA), are some of the best defined biomaterials with regard
to design and performance in drug release in a controlled manner.
For homopolymers, the enantiomeric forms are poly (D-lactic acid)
(PDLA) and poly (L-lactic acid) (PLLA). The physicochemical proper-
ties of optically active PDLA and PLLA are nearly the same, whereas
the racemic PLA has very different characteristics. For example,
racemic PLA and PLLA have Tg’s of 57 and 56 °C, respectively, but
PLLA is highly crystalline with a Tm of 170 °C and racemic PLA is
completely amorphous. Because the naturally occurring lactic acid
is L (or S), PLLA is considered more biocompatible. The polymers
are derived from monomers that are natural metabolites of the
body; thus degradation of these materials yields the corresponding
hydroxy acid, making them safe for in vivo use. PLA–PEG copoly-
mer systems possess surfactant properties because the PEG block
is very hydrophilic and the PLA block is hydrophobic. The inclusion
of PEG in copolymer systems imparts extremely beneficial surface
properties within the body because of the ability to repel proteins
within aqueous environments. This repulsion inhibits the adsorp-
tion of proteins to the polymer surface and, therefore, prevents
many polymer- cell interactions. For example, nanoparticles made
from diblock PLA–PEG copolymers have increased blood circula-
tion times (decreased clearance) in vivo above that of particles
made from PLA alone (Uhrich et al., 1999). Injection molding of
heat-resistant PLA products requires rapid crystallization rates,
which can be achieved by PLA that contains less than 1% D-isomer
and often with the addition of nucleating agents.
Polylactic acid (PLA) has been suggested for the production of
horticultural materials to reduce the environmental problem as a
large quantity of plastic is used in this sector and use as a matrix
for controlled release of herbicides. Chang et al. (1996) evaluated
the impact of PLA in growth stimulation and yield improvement.
Greenhouse studies confirmed that both lactide and PLA increased
soybean leaf area, pod number, bean number and bean and plant
dry weight. This study suggests that use of PLA as an encapsulation
8499
matrix for herbicides could provide reduced environmental impact
and improved weed control and at the same time increasing yield
of soybeans through release of plant growth stimulants in the form
of oligomeric or monomeric lactic acid.
9. PLA – challenges
The main concern of PLA is the price of this polymer. On an
industrial scale, the manufacturing cost of lactic acid monomer will
be targeted to less than 0.8 US$/kg because the selling price of PLA
should decrease roughly by half from its present price of 2.2 US$/
kg. According to the cost analysis the base manufacturing cost of
lactic acid was estimated to be 0.55 US$/kg. There are several is-
sues that need to be addressed for the biotechnological production
of lactic acid, such as the development of high-performance lactic
acid-producing microorganisms and the lowering of the costs of
raw materials and fermentation processes. The biotechnological
processes for the production of lactic acid from cheap raw materi-
als should be improved further to make them competitive with the
chemically derived one (John et al., 2007). One of the major techni-
cal challenges to widespread acceptance of bio-based polymers is
difficulties achieving mechanical and barrier properties compara-
ble with conventional synthetic polymers while maintaining
biodegradability. A barrier to effective commercialization of
bio-based polyesters is their inferior moisture barrier properties
compared to those of synthetic polymers. So management of mois-
ture penetration and hydrolytic degradation of polylactide (PLA) is
extremely important during the manufacturing, shipping, storage,
and end-use of PLA products (Cairncross et al., 2006).
The inherent brittleness of PLA has been a major bottleneck for
its large-scale commercial applications. Numerous approaches
such as plasticization block copolymerization, blending with tough
polymers, and rubber toughening have been adopted to improve
the toughness of brittle polylactide bioplastic. The major draw-
backs of these methods are the substantial decreases in the
strength and modulus of the toughened polylactide. So, a polylac-
tide-based material having good stiffness-toughness balance along
with high bio-based polylactide content is still elusive.
Other main limitations of PLA towards its wider industrial
application are its poor thermal resistance and limited gas barrier
properties which prevent its complete access to industrial sectors
such as packaging (Sinha et al., 2003). Nevertheless, it has been
found (Kiersnowski et al., 2004; and Sinha Ray and Bousmina,
2005) that the above drawbacks can be overcome by the addition
of nanoparticles. PLA based nanocomposites have observed higher
rates of PLA biodegradation in compost by the addition of nanoc-
lays (Paul et al., 2005), which was attributed to the high relative
hydrophilicity of the clays, allowing an easier permeability of
water into the polymer matrix and activating the hydrolytic degra-
dation process. Zhou and Xanthos (2009) from their studies on
nanosize and microsize clay effects on the kinetics of the thermal
degradation of polylactides concluded that, in general, the thermal
stability of PDLLA and its composites is higher than that of PLLA
and its composites and the thermal stability of the nanocomposites
is higher than that of the microcomposites.
Life cycle assessment (LCA), a tool used for measuring environ-
mental sustainability and identifying environmental performance-
improvement objectives. Nature Works TM polylactide (PLA) is a
versatile polymer produced by Cargill Dow LLC. The paper by Vink
et al. (2003) gives an overview of applications of LCA to PLA pro-
duction and provides insight into how they are utilized. The first
application reviews the contributions to the gross fossil energy
requirement for PLA (54 MJ/kg). In the second one PLA is compared
with petrochemical-based polymers using fossil energy use, global
warming and water use as the three impact indicators. The last
application gives more details about the potential reductions in en-
8500 K. Madhavan Nampoothiri et al. / Bioresource Technology 101 (2010) 8493–8501
ergy use and greenhouse gasses. Cargill Dow’s objective is to de-
crease the fossil energy use from 54 MJ/kg PLA down to about
7 MJ/kg PLA. The objective for greenhouse gasses is a reduction
from +1.8 down to 1.7 kg CO2 equivalents/kg PLA. The cellulose
and hemicellulose can be converted into fermentation sugars in a
so-called ‘‘biorefinery”. The lactic acid production process will be
further optimized to increase yield and reduce raw material use
among other improvements and is also a challenge as far as PLA
bulk production is considered.
10. Conclusion
The synthesis of recyclable and degradable polymers having a
highly cross-linked three-dimensional network structure like PLA
is very important for polymer science and technology for support-
ing a green sustainable society. PLA offers a possible alternative to
the traditional non-biodegradable polymers especially when their
recycling is difficult or not economical. Eventhough there are many
limitations due to its material properties, a number of these chal-
lenges are expected to overcome through blending PLA with other
polymers, by making micro- and nanocomposites of PLA, coating
with high barrier materials, and also with polymer modification.
Acknowledgement
The authors are thankful to Department of Biotechnology (DBT)
for the financial support on PLA research.
References
Auras, R., Harte, B., Selke, S., 2004. An overview of polylactides as packaging
materials. Macromol. Biosci. 4, 835–864.
Bendix, D., 1998. Chemical synthesis of polylactide and its copolymers for medical
applications. Polym. Degrad. Stab. 59, 129–135.
Cairncross, R.A., Becker, J.G., Ramaswamy, S., O’Connor, R., 2006. Moisture sorption,
transport, and hydrolytic degradation in polylactide. Appl. Biochem. Biotechnol.
31, 774–785.
Chang, Y.N., Mueller, R.E., Iannotti, E.L., 1996. Use of low MW polylactic acid and
lactide to stimulate growth and yield of soybeans. Plant Growth Regul. 19, 223–
232.
De Jong, S.J., Arias, E.R., Rijkers, D.T.S., Van Nostrum, C.F., Kettenes, J.J.-Van Den
Bosch., Hennink, W.E., 2001. New insights into the hydrolytic degradation of
poly (lactic acid): participation of the alcohol terminus. Polymer 42, 2795–2802.
Drumright, B.R.E., Gruber, P.R., David, E., Henton, D.E., 2000. Polylactic acid
technology. Adv. Mater. 23, 1841–1846.
Franschini, R., Plesu, R., Sarasua, J.R., Prud home, R.E., 2005. Cracking in polylactide
spherulites. J. polym. Sci. Part B: Polym. Phys. 43, 3308–3315.
Gajria, A.M., Dave, V., Gross, R.A., McCarthy, S.P., 1996. Miscibility and
biodegradability of blends of poly (lactic acid) and poly (vinyl acetate).
Polymer 37, 437–444.
Gang, W., Aimin, L., 2008. Thermal decomposition and kinetics of mixtures of
polylactic acid and biomass during copyrolysis. Chin. J. Chem. Eng. 16 (6), 929–
933.
Ghorpade, V.M., Gennadios, A., Hanna, M.A., 2001. Laboratory composting of
extruded poly (lactic acid) sheets. Bioresour. Technol. 76, 57–61.
Gruber, P.R., Hall, E.S., Kolstad, J.J., Iwen, M.L., Benson, R.D., Borchardt, R.L., 1992. US
Patent 5 142 023, US Patent 5 247 058.
Gruber, P.R., Hall, E.S., Kolstad, J.J., Iwen, M.L., Benson, R.D., Borchardt, R.L., 1993. US
Patent 5 247 059, US Patent 5 258 488, US Patent 5 274 073.
Gruber, P.R., Hall, E.S., Kolstad, J.J., Iwen, M.L., Benson, R.D., Borchardt, R.L., 1994. US
Patent 5 357 035.
Gupta, A.P., Kumar, V., 2007. New emerging trends in synthetic biodegradable
polymers – polylactide: a critique. Eur. Polym. J. 43(10), 4053–4074.
Hoffman, A.S., 2002. Hydrogels for biomedical applications. Adv. Drug Deliv. Rev. 43,
3–12.
Hoshino, A., Tsuji, M., Ito, M., Momochi, M., Mizutani, A., Takakuwa, K., 2003.
Biodegradable polymers and plastics. In: Chiellini, E., Solaro, R. (Ed.), Study of
the Aerobic Biodegradability of Plastics Materials Under Controlled Compost,
vol. 47. Plenum Press, New York (Chapter 21).
Huang, M.H., Li, S., Vert, M., 2004a. Synthesis and degradation of PLA–PCL–PLA
triblock copolymer prepared by successive polymerization of 3-caprolactone
and DL-lactide. Polymer 45, 8675–8681.
Huang, S.W., Wang, J., Zhang, P.C., Mao, H.Q., Zhuo, R.X., Leong, K.W., 2004b. Water
soluble and non-ionic polyphosphoester: synthesis, degradation,
biocompatibility and enhancement of gene expression in mouse muscle.
Biomacromolecules 5, 306.
Jacobsen, S., Fritz, H.G., Degee, P., Dutois, P., Jerome, R., 2000. New developments on
the ring opening polymerization of polylactide. Ind. Crops Prod. 11, 265–275.
Jarerat, A., Tokiwa, Y., 2001. Degradation of poly (L-lactide) by a fungus. Macromol.
Biosci. 1, 136–140.
Jarerat, A., Tokiwa, Y., 2003. Degradation of poly (L-lactide) by Saccharothrix
waywayandensis. Biotechnol. Lett. 25, 401–404.
Jarerat, A., Tokiwa, Y., Tanaka, H., 2003. Poly (L-lactide) degradation by
Kibdelosporangium aridum. Biotechnol. Lett. 25, 2035–2038.
John, R.P., Anisha, G.S., Nampoothiri, K.M., Pandey, A., 2009. Direct lactic acid
fermentation: focus on simultaneous saccharification and lactic acid
production. Biotechnol. Adv. 27, 145–152.
John, R.P., Gangadharan, D., Nampoothiri, K.M., 2008. Genome shuffling of
Lactobacillus delbrueckii mutant and Bacillus amyloliquefaciens through
protoplasmic fusion for L-lactic acid production from starchy wastes.
Bioresour. Technol. 99, 8008–8015.
John, R.P., Nampoothiri, K.M., Nair, A.S., Pandey, A., 2005. L (+)-lactic acid production
using Lactobacillus casei in solid-state fermentation. Biotechnol. Lett. 27, 1685–
1688.
John, R.P., Nampoothiri, K.M., Pandey, A., 2006a. Solid-state fermentation for L-lactic
acid production from agro wastes using Lactobacillus delbrueckii. Proc. Biochem.
41, 759–763.
John, R.P., Nampoothiri, K.M., Pandey, A., 2006b. Simultaneous saccharification and
fermentation of cassava bagasse for L (+) lacticacid production using Lactobacilli.
Appl. Biochem. Biotechnol. 134, 263–272.
John, R.P., Nampoothiri, K.M., Pandey, A., 2007. Fermentative production of lactic
acid from biomass: an overview on process developments and future
perspectives. Appl. Microbiol. Biotechnol. 74, 524–534.
Kale, G., Auras, R., Sing, S.P., Narayanan, R., 2007. Biodegradability of polylactide
bottles in real and simulated composting conditions. Polym. Test. 26, 10491061.
Kasuga, T., Fujikawa, H., Abe, Y., 1999. Preparation of polylactic acid composites
containing b-Ca (PO3)2 fibers. J. Mater. Res. 14, 418–424.
Kiersnowski, A., Dabrowski, P., Budde, H., Kressler, J., Piglowski, J., 2004. Synthesis
and structure of poly (e-caprolactone)/synthetic montmorillonite nano-
intercalates. Eur. Polym. J. 40, 2591–2598.
Kopinke, F.D., Remmler, M., Mackenzie, K., Moder, M., Wachsen, O., 1996. Thermal
decomposition of biodegradable polyesters. II. Poly(lactic acid). Polym. Degrad.
Stab. 53, 329–342.
Li, Q., Wang, J., Shahani, S., Sun, D.D.N., Sharma, B., Elisseeff, J.H., 2006.
Biodegradable and photocrosslinkable polyphosphoester hydrogel.
Biomaterials 27, 1027.
Li, S., Tenon, M., Garreau, H., Braud, C., Vert, M., 2000. Enzymatic degradation of
stereocopolymers derived from L-, DL- and meso-lactides. Polym. Degrad. Stab.
67, 85–90.
Lim, L.T., Auras, R., Rubino, M., 2008. Processing technologies for poly (lactic acid).
Prog. Polym. Sci. 33, 820–852.
Lucas, N., Bienaime, C., Belloy, C., Queneudee, M., Silvestre, F., Jose-Edmundo., Nava-
Saucedo., 2008. Polymer biodegradation: mechanism and estimation
techniques – a review. Chemosphere 73, 429–442.
McNeill, I.C., Leiper, H.A., 1985. Degradation studies of some polyesters and
polycarbonates 1. Polylactide: degradation under isothermal conditions,
thermal degradation mechanism and photolysis of the polymer. Polym.
Degrad. Stab. 11, 309–326.
Martin, O., Averous, L., 2001. Poly (lacticacid): plasticization and properties of
biodegradable multiphase systems. Polymer 42, 6209–6219.
Mehta, R., Kumar, V., Bhunia, H., Upadhyay, S.N., 2005. Synthesis of poly (lacticacid):
a review. J. Macromol. Sci. Polym. Rev. 45, 325.
Muller, R., 2008. Biodegradability of polymers: Regulations and methods of testing.
In: Steinbüchel, A. (Ed.), Biopolymers, General Aspects and Special Applications,
vol. 10. Wiley Publishers, pp. 366–388 (Chapter 12).
Murariu, M., Amalia Da Silva Ferreira., Pluta, M., Bonnaud, L., Alexandre, M., Dubois,
P., 2008. Polylactide (PLA)-CaSO4 composites toughened with low molecular
weight and polymeric ester-like plasticizers and related performances. Eur.
Polym. J. 44, 3842–3852.
Narendra, N., Kishore, K., 2002. Hydrolytic degradation and diffusion studies on a
polyphosphate ester. J. Appl. Polym. Sci. 84, 701.
Nijenhuis, A.J., Colstee, E., Grijpma, D.W., Pennings, A.J., 1996. High molecular
weight poly (L-lactide) and poly (ethylene oxide) blends: thermal
characterization and physical properties. Polymer 37, 5849–5857.
Nolasco-Hipolito, C., Matsunaka, T., Kobayashi, G., Sonomoto, K., Ishizaki, A., 2002.
Synchronised fresh cell bioreactor system for continuous L (+) lactic acid
production using Lactococcus lactis IO-1 in hydrolysed sago starch. J. Biosci.
Bioeng. 93, 281–287.
Oda, Y., Yonetsu, A., Urakami, T., Tonomura, K., 2000. Degradation of polylactide by
commercial proteases. J. Polym. Environ. 8, 29–32.
Ohya, Y., Maruhashi, S., Ouchi, T., 1998. Preparation of poly (lactic acid) – grafted
amylose through the trimethylsilyl protection method and its biodegradation.
Macromol. Chem. Phys. 199, 2017.
Ouchi, T., Kontani, T., Ohya, Y., 2003. Modification of polylactide upon physical
properties by solution-cast blends from polylactide and polylactide-grafted
dextran. Polymer 44, 3927–3933.
Park, K.I., Xanthos, M.A., 2009. Study on the degradation of polylactic acid
in the presence of phosphonium ionic liquids. Polym. Degrad. Stab. 94,
834–844.
Paul, A., Delcourt, C., Alexandre, M., Degée, P., Monteverde, F., Dubois, P., 2005.
Polylactide/montmorillonite nanocomposites: study of the hydrolytic
degradation. Polym. Degrad. Stab. 87, 535–542.
 K. Madhavan Nampoothiri et al. / Bioresource Technology 101 (2010) 8493–8501
Pranamuda, H., Tokiwa, Y., 1999. Degradation of Poly (L) Lactide by strains
belonging to genus Amycolaptosis. Biotechnol. Lett. 21, 901–905.
Pranamuda, H., Tsuchii, A., Tokiwa, Y., 2001. Poly (L-lactide)-degrading enzyme
produced by Amycolatopsis sp.. Macromol. Biosci. 1, 25–29.
Reddy, G., Altaf, Md., Naveena, B.J., Venkateshwar, M., Kumar, E.V., 2008. Amylolytic
bacterial lactic acid fermentation – a review. Biotechnol. Adv. 26, 22–34.
Sarasua, J.R., Prud’homme, R.E., Wisniewski, M., LeBorgne, A., Spassky, N., 1998.
Crystallization and melting behavior of polylactides. Macromolecules 31, 3895–
3905.
Schneider and Wilmington, 1955. Properties of high melting lactide. US Patent 2
703 316.
Shah, A.A., Hasan, Fariha., Hameed, Abdul., Ahmed, Safia., 2008. Biological
degradation of plastics: a comprehensive review. Biotechnol. Adv. 26, 246–265.
Sheth, M., Kumar, R.A., Dave, V., Gross, R.A., McCarthy, S.P., 1997. Biodegradable
polymer blends of poly (lactic acid) and poly (ethylene glycol). J. Appl. Polym.
Sci. 66, 1495–1505.
Sinha Ray, S., Bousmina, M., 2005. Biodegradable polymers and their layered silicate
nanocomposites: in greening the 21st century materials world. Prog. Mater. Sci.
50, 962–1079.
Sinha, R.P., Pandey, J.K., Rutot, D., Degee, Ph., Dubois, Ph., 2003. Biodegradation of
poly (e-caprolactone)/starch blends and composites in composting and culture
environment: the effect of compatibilization on the inherent biodegradability of
the host polymer. Carbohydr. Res. 338, 1759–1769.
Sodergard, A., Stold, M., 2002. Properties of lactic acid based polymers and their
correlation with composition. Prog. Mater. Sci. 27, 1123–1163.
Tsuji, H., Ikada, Y., 1992. Autocatalytic hydrolysis of amorphous-made polylactides:
effects of lactide content, tacticity and enantiomeric polymer blending.
Macromolecules 25, 5719.
Tokiwa, Y., Jarerat, A., 2004. Biodegradation of poly (L-lactide). Biotechnol. Lett. 26,
771–777.
Tokiwa, Y., Konno, M., Nishida, H., 1999. Isolation of silk degrading microorganisms
and its poly (L-lactide) degradability. Chem. Lett., 355–356.
8501
Torres, A., Li, S.M., Roussos, S., Vert, M., 1996. Degradation of L and DL-lactic acid
oligomers in the presence of Fusarium moniliforme and Pseudomonas putida. J.
Environ. Polym. Degrad. 4, 213–223.
Toshinori, K., Yoriko, I., Nozomi, I., Yuka, S., 2002. Degradability of biodegradable
plastic (poly (lactic acid)) products. J. Jpn. Soc. Agric. Mach. 64, 115–120.
Tsuji, H., Mizuno, A., Ikada, Y., 1998. Blends of aliphatic polyesters. III.
Biodegradation of solution-cast blends from poly (L-lactide) and poly (e-
caprolactone). J. Appl. Polym. Sci 70, 2259–2268.
Uhrich, K.E., Cannizzaro, S.M., Langer, R.S., ShakeSheff, K.M., 1999. Polymeric system
for controlled drug release. Chem. Rev. 99, 3181–3198.
Vaidya, A.N., Pandey, R.A., Mudliar, S., Suresh Kumar, M., Chakrabarti, T., Devotta, S.,
2005. Production and recovery of lactic acid for polylactide – an overview. Crit.
Rev. Environ. Sci. Technol. 35, 429–467.
Vichaibun, V., Chulavatnatol, M., 2003. A new assay for the enzymatic degradation
of polylactic acid. Sci. Asia 29, 297–300.
Vickroy, T.B., 1985. Lactic acid. In: Moo-Young, (Ed.), Comprehensive Biotechnol.
Pub: DicToronto: Pergamon Press, pp. 761–776.
Vink, E.T.H., Karl, R., Ra’bago, K.R., David, A., Glassner, D.A., Gruber, P.R., 2003.
Applications of life cycle assessment to Nature Works TM. Polylactide
production. Polym. Degrad. Stab. 80, 403–419.
Wang, Y., Li, Y., Pei, X., Yu, L., Feng, Y., 2007. Genome-shufling improved acid
tolerance and L-lactic acid volumetric productivity in Lactobacillus rhamnosus. J.
Biotechnol. 129, 510–515.
Wee, Y.J., Kim, J.N., Ryu, H.W., 2006. Biotechnological production of lactic acid and
its recent applications. Food Technol. Biotechnol. 44, 63–72.
Zhou, Q., Xanthos, M., 2009. Nanosize and microsize clay effects on the kinetics of
the thermal degradation of polylactides. Polym. Degrad. Stab. 94 (3), 327–338.
Zhao, Y.M., Wang, Z.Y., Wang, J., Mai, H.Z., Yan, B., Yang, F., 2004. Direct synthesis of
poly (D, L-lactic acid) by melt polycondensation and its applications in drug
delivery. J. Appl. Polym. Sci. 91, 2143.
Zhao, Z., Wang, J., Mao, H.Q., Leong, K.W., 2003. Polyphosphoesters in drug and gene
delivery. Adv. Drug Deliv. Rev. 55, 483.