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POLYLACTIC ACID: SYNTHESIS,
PROPERTIES AND APPLICATIONS
POLYLACTIC ACID: SYNTHESIS,
PROPERTIES AND APPLICATIONS

VINCENZO PIEMONTE

Nova Science Publishers, Inc.

New York
Copyright © 2012 by Nova Science Publishers, Inc.

All rights reserved. No part of this book may be reproduced, stored in a retrieval system or
transmitted in any form or by any means: electronic, electrostatic, magnetic, tape, mechanical
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Telephone 631-231-7269; Fax 631-231-8175
Web Site: http://www.novapublishers.com

NOTICE TO THE READER

The Publisher has taken reasonable care in the preparation of this book, but makes no expressed or
implied warranty of any kind and assumes no responsibility for any errors or omissions. No
liability is assumed for incidental or consequential damages in connection with or arising out of
information contained in this book. The Publisher shall not be liable for any special,
consequential, or exemplary damages resulting, in whole or in part, from the readers’ use of, or
reliance upon, this material. Any parts of this book based on government reports are so indicated
and copyright is claimed for those parts to the extent applicable to compilations of such works.

Independent verification should be sought for any data, advice or recommendations contained in
this book. In addition, no responsibility is assumed by the publisher for any injury and/or damage
to persons or property arising from any methods, products, instructions, ideas or otherwise
contained in this publication.

This publication is designed to provide accurate and authoritative information with regard to the
subject matter covered herein. It is sold with the clear understanding that the Publisher is not
engaged in rendering legal or any other professional services. If legal or any other expert
assistance is required, the services of a competent person should be sought. FROM A
DECLARATION OF PARTICIPANTS JOINTLY ADOPTED BY A COMMITTEE OF THE
AMERICAN BAR ASSOCIATION AND A COMMITTEE OF PUBLISHERS.

LIBRARY OF CONGRESS CATALOGING-IN-PUBLICATION DATA

ISBN 978-1-62100-348-9

Published by Nova Science Publishers, Inc. ; New York

 CONTENTS

Vincenzo Piemonte

Preface i
Chapter 1 Properties of Plastics and Composites Prepared From Different
Sources/ Grades of PLA Error! Bookmark not defined.
Chapter 2 Poly(lactic acid) Polymer Blends A Review of Recent WorksError! Bookmark not defined.
Chapter 3 Melt Processing of Poly(Lactic Acid): Morphology, Mechanical
Behavior, Thermal Stability and Kinetics of the Thermal
Decomposition Error! Bookmark not defined.
Chapter 4 Improvement of Mechanical Properties and Processability by
Addition of Polyesters Error! Bookmark not defined.
Chapter 5 Filler-Matrix Compatibility of Poly(Lactic Acid) Based
Composites Error! Bookmark not defined.
Chapter 6 Properties and Biodegradation of PLA and
PLA/Nanocomposites Error! Bookmark not defined.
Chapter 7 Modeling Hydrolytic Degradation of PLA DevicesError! Bookmark not defined.
Chapter 8 New Perspectives for Application of PLA in Cultural HeritageError! Bookmark not defined.
Chapter 9 Flash Co-Pyrolysis of Biomass with Polylactic Acid – Statistical
and Comparative Analytical InvestigationError! Bookmark not defined.
Chapter 10 Synthesis of Polylactic Acid for Biomedical, Food Packaging
and Structural Applications: A Review 5
Chapter 11 Engineering Polylactic Acid with Thermal-Responsive Shape
Memory Effect for Biomedical ApplicationsError! Bookmark not defined.
Chapter 12 Preparation and Applications of Poly (lactide acid) Microsphere
and Microcapsules for Drug Delivery Error! Bookmark not defined.
Chapter 13 Drug–Loaded Microspheres of Poly(D,L-Lactide) and Poly(D,L-
Lactide-Co-Glycolide) Polymers Prepared by Spray-Drying:
Characterization and In Vivo AdministrationError! Bookmark not defined.
Chapter 14 Bioengineering Applications of Ultra-Thin Poly(Lactic Acid)
Nanofilms Towards Cell-Based Smart BiomaterialsError! Bookmark not defined.
Index Error! Bookmark not defined.
 PREFACE

In past few years, due to the increase of environmental pollution and global worming, the
development of systems based on sustainable use of materials has accelerated. Particularly
interesting is the effective usage of the limited carbon resources and the conservation of the
energy resources. In this framework, bio-based polymers, made from biomass, can play an
important role.
The reasons of the growing interest in the development of biodegradable plastics are
environmental and strategic. As a matter of fact, in order to reduce the environmental impact
of plastics (especially in terms of CO2eq released in the environment) some of the products
obtained from agriculture (starch, cellulose, wood, sugar, etc.) are used as raw materials. This
way the net balance of carbon dioxide is reduced since growing bioplastic feedstocks remove
carbon dioxide from the atmosphere. Furthermore, petroleum, with a constantly rising price,
is replaced by renewable raw materials obtained from agriculture.
In some countries, the adoption of bioplastics was also stimulated by other environmental
reasons, related to the issue of waste disposal: in the 1990s, the municipal solid waste in Italy
(with a fraction of plastics equal to 20–30%) was usually disposed in landfills. Traditional
plastics undergo degradation phenomena with very slow kinetics; hence, the volume occupied
by these materials in landfills is virtually stable over time. On the other hand, bioplastics
show higher degradation rates in landfills and, therefore, the required volumes can be
reduced.
It is worth highlight that the word ‘‘bioplastic’’ is actually ambiguous, because it can
refer simultaneously to two different aspects, which are not necessary connected. In fact, it
can refer to the source (renewable) used as raw material for bioplastics or to the
biodegradability and/or compostability that foreshadows a specific final destination of the
bioplastics. Furthermore, a plastic based on renewable sources (biobased) may not be
biodegradable (i.e. polyethylene (PE) obtained from bioethanol) or may be biodegradable but
obtained from nonrenewable sources (e.g., polycaprolactone). Finally, there are also
bioplastics that are both biodegradable and bio-based such as polylactic acid (PLA), which
represents a solution for the need of environmentally-friendly packaging materials (produced
from renewable sources) and biodegradable plastics with a low environmental impact.
Although PLA has been produced for several decades, its use was limited to biomedical
application (e.g. biocompatible sutures, prostheses, biologically active controlled release
devices) because of the high cost. The breakthrough occurred in the early 1990s when Cargill
 ii Vincenzo Piemonte

Inc. succeeded in polymerizing high molecular weight PLA using a commercially viable
lactide opening reaction. Since then, the scientific interest on the PLA has grown
exponentially over the years, together with the importance that it has acquired on the market.
Nowadays, thanks to its unique features in terms of versatility and reliability, PLA is the most
important and most used bioplastic in the world.
This book will appeal to all the readers who not only want to have a reference book of
consolidated notions on PLA, but also, and especially, to those who want to discover new
potentials and new application fields of this unique biodegradable polymer.
The book describes the synthesis, properties and applications of PLA through 14 original
and very interesting chapters that will guide the reader through a fascinating journey into the
world of the PLA, providing interesting insights for those who intend to use this polymer for
innovative applications, or simply those who want learn more about this very important
biodegradable and bio-based plastic.
The book starts with an overview of the different types of PLA which are now available
on the market and mechanical characteristics and properties, strengths and weaknesses of
PLA are reported. Then the book continues with chapter 2, where the reader can find an
useful review of the different production techniques of PLA-based copolymers, at the aim of
extending the already broad range of applications of this biopolymer. Chapters 3 and 4 are
intended to give a better insight of the PLA processability, through the analysis of mechanical
behaviour, thermal stability and kinetics of thermal decomposition of PLA. Some possible
techniques for improving the mechanical properties and processability of PLA by adding
polyesters are also presented and discussed.
The creation of composite materials that can meet the most demanding users'
expectations is certainly a very important field and therefore, in this book some chapters will
be devoted to this subject. Through chapters 5 and 6 the reader will know the great potentials
of the PLA in the construction of composites and nanocomposites, appreciating the great
versatility of this polymer.
At the beginning of this preface it has been mentioned that the PLA is not only a bio-
based plastic: its biodegradability introduces this polymer in a world of eco-friendly and
human-friendly applications in several technological fields. Therefore, chapter 7 is dedicated
to deepen the PLA degradation, delving into the hydrolysis mechanisms which are the basis
of the PLA biodegradability.
After chapter 7, the reader is catapulted into the fascinating world of PLA applications,
ranging from environment to the biomedical fields, from pharmaceutical to food industry, to
go up to the conservation of cultural heritage.
Particularly, in chapter 8 a comprehensive survey of conservation materials and the most
relevant achievements related to the application of PLA in conservation of cultural heritage
are reported and discussed, while chapter 9 deals with the end of life of PLA by analysing the
flash co-pyrolysis of biomass with polylactic acid through a statistical and comparative
analytical investigation.
Chapters from 11 to 14 are dedicated to PLA applications in the pharmaceutical and
biomedical fields, introduced by a review reported in chapter 10 on interesting applications of
PLA in biomedical, food packaging and structural fields. Then, chapter 11 reviews recent
progress in engineering PLA-based thermal-responsive shape memory polymers and
discusses their potential and limitations for biomedical applications. Chapters 12 and 13 are
 Preface iii

devoted to the investigation of the production of PLA microcapsules for drug delivery with
different techniques.
The fascinating journey on the PLA world concludes with chapter 14, which describes
the preparation methods to obtain PLA structures with a nanometric thickness and a large
surface area. The main features of such devices and the possibilities of functionalizing them
by the inclusion of nanoparticles with targeted physical properties in the polymeric matrix are
presented.
Finally, let me conclude this preface by thanking all the authors who have contributed to
the realization of this book, without whom this project would have never been born. I thank
them for their participation and patience during the preparation of this book and I am grateful
that they have entrusted me to edit their contributions. I hope the readers will find this book
useful. I am looking forward to receive comments and constructive feedbacks about contents.
4 Tom Cornelissen, Geert Molenberghs, Mark Stals, et al.
Chapter 10

SYNTHESIS OF POLYLACTIC ACID FOR BIOMEDICAL,

FOOD PACKAGING AND STRUCTURAL
APPLICATIONS: A REVIEW

Mohammad S. Islam
Institute of Polymer and Composites, The University of Minho, Portugal

ABSTRACT
Interest in bio-polymers from natural resources such as plants, stems largely from
increasing regulation and public concern on ecological issues and the need for sustainable
alternatives to finite petrochemical products. Performance of bio-polymers can be
obtained as good as synthetic polymers but with several environmental advantages: they
create almost no toxic emissions; their raw materials are sustainable, renewable and
widely grown. Over the last decade polylactic acid (PLA) has been one of the most
promising biopolymers and better manufacturing practices have improved the economics
of producing lactic acid monomer through fermentation of renewable resources like corn,
sugar beet and sugarcane. In addition to being thermoplastic, biodegradable,
biocompatible and compostable, PLA shows good mechanical and barrier behavior and it
has the ability to reinforce fillers. This chapter gives a review of available literatures on
the production sources of PLA, provides information on its synthesis routes and deals its
interesting applications in biomedical, food packaging and structural fields.

1. INTRODUCTION
Management of solid waste consists of polymeric materials from petrochemical resources
such as thermoplastics (e.g. products of polyethylene terephthalate, polypropylene and
polyethylene) and thermosets (e.g. products of synthetic rubbers, phenolic and epoxy resins)
is an important worldwide problem. There are high capital and operating costs as well as
environmental pollution problems associated with incineration. Used dumped polymeric
materials such as plastic bottles and containers, tyres and electric switches have slow or
nominal degradation in the landfill. The landfills are limited and dumped polymeric materials
 6 Mohammad S. Islam

contain toxic materials such as lead and cadmium which were used as colorants, stabilizers
and plasticizers during their production. These toxic materials may leach to the soil and
impose serious environmental risk [1]. Moreover, petrochemical resources are progressively
diminishing and the oil prices are radically increasing. All of these issues add with increasing
consumer interest in sustainable green products and have sparked research and development
in favor of biodegradable polymeric materials from renewable resources. Polylactic acid or
polylactide (PLA) belongs to the family of aliphatic polyesters is one of the most widely used
biodegradable materials [2-6] manufactured from lactic acid that in turn is produced from
renewable resources such as corn, sugarcane and rice [7]. Besides being biodegradable and
having produced from renewable resources, PLA provides numerous other benefits including:
fixation of carbon dioxide, a greenhouse gas [8]; significant amount of energy savings [9];
improvement of farm economies [10] and manipulation of physico-mechanical properties
using polymer architecture such as orientation, blending, branching, cross-linking, or
plasticization [11-15]. Figure 1 shows the novel ecologically friendly life cycle of PLA.

Figure 1. Novel ecologically friendly life cycle of PLA.

Although production processes for lactic acid and PLA are well known [16-21], very few
processes have been commercialized [18] and still the cost of PLA is not very competitive
with synthetic plastics [19, 22]. The core of PLA production technology is the fermentative
production of lactic acid and its recovery [19, 22]. Many processes are reported in the
literature for the recovery of lactic acid [23-26] and still offer an extensive scope for research
and development. In addition to being biodegradable, PLA has many favorable properties
such as good biocompatibility and bioresorbability [27-30], barrier properties [10, 18],
mechanical strength [31, 32] and the ability to reinforce fillers [33, 34]. All of these properties
make it a polymer of choice for biomedical (e.g. implants, sutures, drug encapsulation), food
packaging (e.g. food wrap, container, drinking cups) and structural applications (e.g. civil
structures, furniture, marine, automobiles). This chapter deals with production sources (i.e.
 Synthesis of Polylactic Acid for Biomedical, Food Packaging, Structural Applications7

raw materials), synthesis routes and its applications in biomedical, food packaging and
structural fields.

2. POLYLACTIDE: SOURCES AND SYNTHESIS ROUTES

OF PRODUCTION

Currently, PLA is synthesized by a two-step process consisting of (i) lactic acid

production by chemical synthesis from petroleum resources or mainly fermentation of
environment friendly renewable resources or (ii) polymerization of lactic acid by direct
condensation or solvent-based azeotropic dehydrative condensation and ring opening
polymerization of lactide, a cyclic dimer resulting from the dehydration of lactic acid.

2.1. Sources of Production: Lactic Acid as a Precursor

The industrial scale production of lactic acid (α-hydroxypropionic acid), started at the
end of nineteenth century to be used mainly in food industry as an acidity regulator although
it had uses in pharmaceutical, cosmetic, leather and textile industries [18, 35]. Recently, there
has been a renewed interest in lactic acid production because it is the monomeric precursor of
PLA [36]. It is generally obtained either by chemical synthesis from petroleum feed stocks
(could produce racemic DL-lactic acid only) or by renewable carbohydrate fermentation
(could produce an optically pure L(+) or D (-) lactic acid stereoisomer) [37]. The physical
properties of PLA depend on this isomeric composition [38, 39]. Therefore, for PLA
production fermentative pathway is desirable not only as a renewable resource, but also to
obtain desired physical properties.
Over the years several authors have studied a large number of carbohydrates for
production of lactic acid [40-44]. Their investigations were on the basis of the increase of the
yield of lactic acid, optimization of the production of biomass, minimization of the formation
of by product, enhancement of the rate of fermentation, reduction of any pre-treatments
involved, ease of availability and reduction of costs involved [45].
In the USA, corn is the cheapest starch-rich and most widely available annually
renewable resource from which lactic acid is produced. In other parts of the world, locally
available crops such as rice, cottonseed hull, grapefruit, sugar beets, sugarcane, wheat and
sweet potatoes can be used as a starch/sugar feedstock [7, 45]. Conversion technologies to
facilitate the use of lignocellulosic biomass feedstocks, such as corn stover (stover refers to
stalks, leaves and cobs that remain in corn fields after the grain harvest to revitalize the soil),
grasses, wheat and rice straws, and bagasse (the pulpy residue of sugarcane) have also been
investigated [7]. Effort has been given to develop microbial processes for the production of
high purity L (+) lactic acid at low cost from sago starch which is in abundance in Sarawak,
Malaysia and Indonesia [45]. Lactic acid has also been produced by simultaneous
saccharification and fermentation of pre-treated alpha fibre [45].
Although for the renewable sources to be converted to lactic acid, most investigations
have paid attention to the carbohydrates, the finicky nature of lactic acid bacteria is still the
main hurdle to the economical feasibility of the fermentation process. The fermentation
 8 Mohammad S. Islam

processes to obtain lactic acid can be classified into two types namely, heterofermentative and
homofermentative depending on the type of bacteria used. In the heterofermentative method
less than 1.8 moles of lactic acid per mole of hexose is produced along with significant levels
of other metabolites such as acetic acid, ethanol, glycerol, mannitol and carbon dioxide. In the
homofermentative method an average of 1.8 moles of lactic acid per mole of hexose and
minor levels of other metabolites are produced [10]. Most lactic acid bacteria require a wide
range of growth factors including amino acids, vitamins, fatty acids, purines, and pyrimidines
for their growth and biological activity [46, 47] and the more supplemented the medium, the
higher the productivity of the lactic acid could be obtained. Among the various complex
nitrogen sources for lactic acid fermentation (e.g. yeast extract, malt sprouts, peptones, grass
extract, N-Z-case plus, corn steep liquor, N-Z-amine YT, casein hydrolysate, distiller’s waste,
ammonium phosphates, beef extract, urea, whey permeate and soybean hydrolysate) [45, 48,
49] that have been studied thus far, yeast extract is the best choice for both microbial growth
and lactic acid production [50-53]. However, for the production of lactic acid as a source for
commodity chemicals, yeast extract is not cost effective [54, 55]. Therefore, efforts have been
given to use other sources of growth factors from industrial byproducts to achieve a partial or
total replacement of yeast extract [56-59].

2.2. Synthesis Routes of Production

Synthesis of PLA can be obtained generally by two routes, namely (i) direct condensation
of lactic acid [16, 60] and (ii) ring-opening polymerization (ROP) of lactide (a cyclic dimmer
of lactic acid) [39, 61] as shown in Figure 2. In ROP route, either D-lactic acid, L-lactic acid,
or a mixture of the two are prepolymerized to obtain an intermediate low molecular weight
poly(lactic acid), which is then depolymerized into a mixture of lactide stereoisomers. Lactide
is generally formed by the condensation of two lactic acid molecules as follows: L-lactide
from two L-lactic acid molecules, D-lactide from two D-lactic acid molecules, and meso-
lactide from one L-lactic acid and one D-lactic acid molecule. After purification the lactides
are polymerized into high molecular weight PLA with a constitutional unit of
[OCH(CH3)CO]– [20, 62, 63]. Melting point, mechanical strength and crystallinity of PLA
are determined by different proportions of L, D, or meso-lactide and the molecular weight are
determined by the proper addition of hydroxylic compounds. PLA can be produced so that it
is totally amorphous or up to 40% crystalline by the proportion of D and L-lactides. PLA
containing more than 93% L-lactic acid are semicrystalline while PLA with 50–93% L-lactic
acid are strictly amorphous [63]. The presence of both meso- and D-lactide forms in the PLA
introduces sufficient irregularity to limit crystallinity. Moreover, the presence of meso-lactide
in the PLA structure produces a depression of the melting temperature (Tm) as follows: Tm
(oC) ≈ 175oC–300Wm, where Wm is the fraction of meso-lactide and 175oC is the melting
temperature of PLA made of 100% L-lactide [63]. The glass transition temperature (Tg) of
PLA is also determined by the proportional presence of different lactides in the PLA. This
results in PLA polymers with a wide range of hardness and stiffness values. Generally, the Tg
of PLA ranges from 50 to 80oC while the Tm ranges from 130 to 180oC [64]. Since direct
condensation route is an equilibrium reaction, the achievable molecular weight using this
route may become limited due to the difficulties of removing trace amounts of solvent such as
water at the end of the polymerization process due to hydrolysis of ester bonds [19].
 Synthesis of Polylactic Acid for Biomedical, Food Packaging, Structural Applications9

Thus, although direct condensation is the least expensive route [18], other approaches
such as azeotropic dehydration to remove most of the condensation water in the direct
esterification process have been assessed [18, 65]. However, most work has been focused so
far on the ring opening polymerization of lactide for the production of pure high molecular
weight PLA [18, 19].

Figure 2. Synthesis routes of PLA [20].

2.2.1. Synthesis by Direct Condensation of Lactic Acid

PLA produced by direct condensation of lactic acid is a brittle polymer and generally
unusable [18]. This polymerization technique has some other drawbacks including need for
large reactor, evaporation, solvent recovery and increased racemization [66]. Although PLA
can be synthesized with molecular weight of over 1 × 105 by direct condensation of lactic
acid [30, 60]. The use of chain coupling agent or esterification promoting adjuvents to
increase the molecular weight of PLA adds cost and complexity to the process [20, 67-70].
The function of chain coupling agent is to react with either the hydroxyl (OH) or the carboxyl
(COOH) end-groups of the PLA [10, 20, 71]. The advantages of esterification promoting
adjuvents are that the final product is highly purified and free from residual catalysts and
oligomers [18]. To produce high molecular weight PLA without the use of chain coupling
agents or adjuvents and the drawbacks associated with them, azeotropic dehydration or
azeotropic condensation polymerization method is employed by Mitsui Chemicals, Japan [18,
72]. In this method, the monomer lactic acid and a catalyst are dehydrated azeotropically in a
high boiling, refluxing and aprotic solvent under reduced pressure to obtain high molecular
weight PLA (Mw ≥ 300,000) [20, 73]. This polymerization method gives considerable amount
of catalyst residue which may cause degradation and hydrolysis during processing. For
biomedical applications, this residual catalyst is deactivated or precipitated and filtered out
[18]. The molecular weight of PLA is of critical importance for the type of biomedical
 10 Mohammad S. Islam

application. Generally, the construction of screws and plates for use as orthopedic implants
needs material with high Young’s modulus with molecular weight in the area of several
hundreds of thousand [74]. On the other hand, mechanical strength is not of particular
importance for the preparation of slabs for use in controlled release but requires proper
biodegradation characteristics and low melting point for ease of the drug incorporation with
molecular weights in the area of 2–3 × 103 [75]. Henton et al. reported that high molecular
weight PLA is naturally resistant to supporting bacterial and fungal growth, which allows its
safe use in food packaging and sanitation [19].

2.2.2. Ring Opening Polymerization of Lactide

Ring-opening polymerization (ROP) of lactide is the established and preferred route for
the large scale production of high molecular weight PLA (Mw ≥ 100,000) especially in
various commercial processes [10, 21, 71, 76]. For ROP of lactide, many catalyst systems
have been assessed to increase the reaction productivity including metallic, organometallic,
inorganic and organic complexes of aluminum, zinc, tin, and lanthanides [19, 20, 70, 77, 78].
Even strong bases such as metal alkoxides have also been used with success to some extent
[19]. Depending on the catalyst system and reaction conditions, many mechanisms such as
cationic [79], anionic [80] and coordination [81, 82] have been proposed to explain the
kinetics, side reactions, and nature of the end groups observed in ROP of lactide [19, 83].
Among the studied catalyst systems, tin compounds, especially tin (II) bis-2-ethylhexanoic
acid (stannous octoate, Sn(Oct)2) which is approved by the US Food and Drug Administration
[84], are preferred for the bulk polymerization of lactide due to their solubility in molten
lactide, high catalytic activity, low toxicity and ability to give high molecular weight with low
rate of racemization of the polymer [19, 85]. The mechanism of ROP with Sn(Oct)2 has been
studied by many authors [86-88] and a comprehensive discussion of all mechanism is
available in [83]. For the polymers to be used for medical applications even traces of the
catalyst that remain in the system must be removed [21].
In addition to producing PLA by two step process as discussed above, many researchers
have also attempted to improve the material properties of PLA by copolymerization or
blending with other polymers [89-92]. Despite these efforts, existing chemical methods are
not effective considering the availability of lactonized monomers used in copolymerization
and their cost. Yang et al. [93] have reported for the first time a one-step fermentative
production process of PLA and its copolymers containing various lactate fractions from
renewable resources. They have described that PLA and its copolymers containing various
lactate fractions can be produced in recombinant Escherichia coli (E. coli) by establishing
heterologous pathways employing evolved Clostridium propionicum propionate CoA
transferase (PctCp) and Pseudomonas sp. MBEL 6-19 polyhydroxyalkanoate (PHA) synthase
1 (PhaC1Ps6-19). As E. coli cannot supply (D)-lactyl-CoA, which is a monomer required for
the synthesis of PLA, evolved PctCp was introduced to generate (D)-lactyl-CoA more
efficiently. PHA synthase was also evolved to accept (D)-lactyl-CoA more preferentially as a
substrate by rational design and saturation mutagenesis. In the second consecutive study of
Yang et al. [94], the metabolic pathways of E. coli were further engineered by knocking out
the ackA, ppc, and adhE genes and by replacing the promoters of the ldhA and acs genes with
the trc promoter based on in silico genome-scale metabolic flux analysis in addition to
rational approach. Using this engineered strain, they have showed that from glucose, PLA
homopolymer could be produced up to 11 wt% and P(3HB-co-LA) copolymers containing 70
 Synthesis of Polylactic Acid for Biomedical, Food Packaging, Structural Applications11

mol% lactate could be produced up to 46 wt%. From glucose and 3HB, P(3HB-co-LA)
copolymers containing 55–86 mol% lactate could be produced up to 56 wt% by introducing
the Cupriavidus necator b-ketothiolase and acetoacetyl-CoA reductase genes. Thus, the
strategy of combined metabolic engineering and enzyme engineering has allowed efficient
bio-based one-step production of PLA and its copolymers. They have expected that this
strategy should be generally useful for developing other engineered organisms capable of
producing various unnatural polymers by direct fermentation from renewable resources.

3. PLA IN BIOMEDICAL APPLICATIONS

PLA has high mechanical properties and excellent shaping and molding properties [32].
It is biocompatible (which means it has good blood and tissue compatibility, and if slow
degradation takes place, the degradation products are non-toxic) as well as bioresorbable
(which means it can be broken down by the body and does not require mechanical removal)
in the human body [18, 95]. Therefore, it is considered as one of the most important
biodegradable polymers investigated for a wide range of biomedical and pharmaceutical
applications such as controlled drug release, resorbable prostheses, biodegradable sutures,
medical implants and scaffolds for tissue engineering [96-98].
The molecular weight of the polymer material directly influences the mechanical and
sorptive properties of PLA and hence critical depending on the end use [99, 100]. High
molecular weight polymer material is necessary for applications such as bone plates or
temporary internal fixation of broken or damaged bones [21]. For being bioresorbable, PLA
including other biodegradable polymers have been shown to be advantageous over the
conventional polymers in case of parenteral controlled release systems [21]. The preparation
of slabs for use in controlled release does not require high strength. Therefore, low molecular
weight material can be used having the advantage of favorable degradation behavior in the
human body. PLA has been used thus far as a drug carrier in the form of microcapsules [101,
102], microspheres [103], pellets [104] and tablets [105-108] for the administration of
antimycobacterial drugs, quinolones, anti malarial drugs, antiinflammatory drugs, antitumor
agents, hormones and fluoride containing tablets for oral use [21].
PLA can be reinforced with non-resorbable materials such as carbon fibres to achieve
carbon fibre/PLA composites of high mechanical properties before the implantation [18]. The
long term effects of resorbed materials in the living tissues are not completely known and are
concerns yet to be resolved [109].
Materials from PLA and its copolymers have been designed to replace metal and other
non-absorbable polymers as therapeutic aids in surgery, including pins [110], plates [111],
screws [111, 112], suture anchors [113], and intravascular stents [114, 115]. Other medical
applications currently being practiced include dressings for burn victims [116], substrates for
skin grafts [110] and dental applications [114].
 12 Mohammad S. Islam

4. PLA AS FOOD PACKAGING MATERIALS

PLA has a great opportunity to displace less environmentally benign materials in the area
of packaging because it has favourable physical properties such as transparency, high elastic
modulus and high melting temperature which often improves function as well as diminish
environmental impact [113, 117]. It is also medically proven as a safe material for food as the
level of lactic acid that migrates to food from packaging materials is much lower than the
amount of lactic acid used in common food ingredients [118]. However, as a packaging
material, initially PLA has found its application in high value films, rigid thermoforms,
coated papers and food and beverage containers because of its higher cost. PLA may find its
packaging applications for a broader array of products [119-122] as modern and emerging
production technologies lower its production costs [36, 119, 120, 123]
By providing consumers with extra end-use benefits, such as meeting environmental
regulations, PLA has become a growing alternative as a packaging material for demanding
markets [10]. PLA can be used as a food packaging polymer for short shelf life products such
as fruit and vegetables. PLA also has common packaging applications such as containers,
drinking cups, sundae and salad cups, overwrap and blister packages [124, 125]. PLA can be
processed in traditional polymer processing operations such as injection molding, blow
molding, extrusion, and extrusion coating. As a result, lids, trays, and clamshells used in food
handling can be thermoformed from extruded sheet PLA, even yielding products with higher
flex-crack resistance in living hinges than those made of polystyrene [113]. The
thermoformed PLA containers are also being used in retail markets for fresh fruit and
vegetables [126, 127]. Disposable cutlery can also be produced using injection molding of
PLA [113].
Films are one of the largest application areas for PLA. The ability to be stress and thermo
crystallized and also the ability to modify the crystallization kinetics and physical properties
for a wide variety of applications by incorporation of D-or meso-co-monomer, branching, and
change of molecular weight makes PLA an extremely versatile commodity polymer. Films
are transparent when stress crystallized and have acceptance by customers for food contact.
PLA films can be prepared by blown double bubble technology or by cast-tentering. The
films obtained from cast-tentering have many properties desirable for consumer food
packaging such as very low haze, excellent gloss, and good gas (O2, CO2, and H2O)
transmission rates. For twist wrap packaging, PLA films have superior dead fold or twist
retention [19].
Thin sheets of many PLA variants possess high gloss, excellent heat sealability and
clarity, allowing extruded thin sheets of PLA to replace cellophane and polyethylene
terephthalate (PET) in transparent packaging [128]. Tough and puncture resistant bags for
yard and/or food wastes form another set of applications in which not only the physical
properties but also the biodegradable nature of PLA can be used to advantage. The
biodegradable characteristic helps the bags to degrade within 4-6 weeks in a composting
environment [128].
 Synthesis of Polylactic Acid for Biomedical, Food Packaging, Structural Applications13

5. STRUCTURAL APPLICATIONS/COMPOSITES PRODUCTION OF PLA

The use of traditional composites made of glass, aramid or carbon fibre with synthetic
polymers of petrochemical origin have been used for aerospace, defense, marine, automotive,
civil infrastructure and sporting goods for more than two decades for their high strength and
stiffness, dimensional stability, and thermal properties [129, 130]. However, finite nature of
the synthetic polymers and fibres and due to new imperatives on environmental pollution, the
focus of the researchers is shifted to bio-composites based on natural resources with the
application areas remaining the same [131, 132]. Bio-composites made of biopolymers (e.g.
PLA, cellulose esters, polyhydoxyalkanoates and starch) and natural fibres (such as flax,
hemp, kenaf, jute or cotton) are generally biodegradable and are important research and
development achievements [133].
LA is one of the most important types of biopolymer (produced with a capacity of over
140,000 tons per year) which can be used in the biocomposites production because of its
biodegradability and maintained mechanical properties without rapid hydrolysis during use.
PLA is expensive in comparison to conventional thermoplastics and they are sometimes too
weak for some applications especially the inherent brittleness of PLA has been the main
obstacle to expanding its commercial use. To reduce the cost and also to improve the
properties of the material PLA without interfering its ‘‘green polymer” image, many
researchers [33, 134, 135] have investigated natural fibre reinforced PLA bio-composites for
structural applications.
Graupner et al. [136] described the production and the mechanical characteristics of
composites (which maybe used for different components in automobiles as per equipment) of
different types of natural fibres like cotton, hemp, kenaf and man-made cellulose fibres like
lyocell with PLA. They reported that kenaf and hemp fibre bundles, as well as their mixtures,
could significantly increase the tensile strength and Young’s modulus of composites, but
lower the impact strength of the pure matrix significantly. One the other hand, they reported
that lyocell/PLA composites showed better tensile and impact characteristics and hence, could
be used for interior parts of automobiles or safety helmets at the compromise of price. Bodros
et al. [137] reported the possibility of substituting a frequently used polyester/glass fibre
laminate by a PLA/flax fibre biocomposite for applications where the composite structure
undergoes mechanical stress by tensile loading. Over the years, mechanical performance of
natural fibre-reinforced PLA have been investigated with different types of fibres like kenaf,
jute, flax abaca, hemp and cordenka rayon fibres with various types of short and long fibres,
unprocessed and processed fibres, untreated and treated fibres, random and aligned fibres and
non-woven and woven fibres for structural applications [33, 133-135, 138-140]. Other natural
fillers such as rice straw fibres, wood flour, sugar beet pulp, rye husk and wheat husk have
also been investigated with PLA for improved mechanical performance in order to be used in
structural applications [34, 141-143].

6. CONCLUSION
PLA is a widely used material for medical application for decades. Recently, it has
gained a huge credibility for food packaging application and a more recent progression
 14 Mohammad S. Islam

towards green products has led to its development as a replacement of synthetic polymers in
the production of biocomposites for structural applications. However, there still are certain
features which limit the commercialization of PLA such as thermal instability, moisture
permeation, processing conditions and inefficient technology.
The greatest obstacle to greater market penetration of PLA is its high production cost.
Indeed, reduction of production cost is a necessity for its further widespread applications.
However, increasingly higher oil prices and progressive dwindling of fossil resources are
enabling PLA to compete directly with the polymers from petroleum resources.
The use of PLA as a cost-effective alternative to commodity petrochemical-based
polymers will increase demand for products from renewable resources such as corn and sugar
beets, and is an advanced example of sustainable technology. PLA is finding its rapid growth
and expansion in the areas including blends of PLA, copolymers, and impact-modified
products which are creating opportunities in the invention of unlimited new products. As we
move forward, like PLA, increased cost-effective utilization of renewable resources will be
one of the strong drivers for sustainable products with emphasis on reduced energy
consumption, waste generation, and emission of greenhouse gases.

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