Ijacv13n2 02
Ijacv13n2 02
Biodegradable Polymers
Abstract
INTRODUCTION
Synthetic plastics are resistant to degradation, and subsequently their disposal is
stimulating a global drive for the establishment of biodegradable polymers. As the
development of these materials rises, industry must discover unique applications of
them. Material usage and final mode of biodegradation are reliant on the composition
180 Rummi Devi Saini
BIODEGRADABILITY OF MATERIALS
The American Society for Testing of Materials (ASTM) and the International
Standards Organization (ISO) define degradable plastics as those which undergo a
significant change in chemical structure under specific environmental conditions [11].
These changes result in a loss of physical and mechanical properties. Biodegradable
plastics suffer degradation from the action of naturally occurring microorganisms
such as bacteria, fungi and algae. Plastics are also categorized as photodegradable,
oxidatively degradable, hydrolytically degradable, or those which may be composted.
Usually, the adherence of microorganisms on the surface of plastics followed by the
occupation of the exposed surface is the main mechanisms taking place in the
microbial degradation of plastics. The enzymatic degradation of plastics by hydrolysis
occurs by a two-step process. In the first step, the enzyme binds to the polymer
substrate and then catalyses a hydrolytic cleavage of the polymer. Polymers get
degraded into low molecular weight oligomers, dimers and monomers and lastly to
CO2 and H2O. The degradation potential of various microorganisms towards a
polymer is usually assessed by using a clear zone method with agar plates. Agar
Biodegradable Polymers 181
plates having blended polymers are injected with microorganisms. These polymer-
degrading microorganisms excrete extracellular enzymes that diffuse through the agar
and then degrade the polymer into water soluble substances. Using this technique, it
was observed that poly (hydroxybutyrate) (PHB), polypropiolactone (PPL) and
Polycaprolactone (PCL) degraders are extensively dispersed in diverse environments
[12-14]. Most of the strains which are able to degrade PHB belong to different
taxonomy such as Gram-positive and Gram-negative bacteria, Streptomyces and fungi
[13]. About 39 bacterial strains of the classes Firmicutes and Proteobacteria have
been reported to degrade PHB, PCL, and PBS, but not PLA [14]. Only a few
microorganisms have been isolated and identified which can degrade PLA. In the
different ecosystems the population of aliphatic polymer-degrading microorganisms
have been found to be in the following order: PHB = PCL > PBS > PLA [12, 15].
STRUCTURE
Biodegradable polymers comprise ester, amide, or ether bonds. In general,
biodegradable polymers can be grouped into two large groups on basis of their
structure and synthesis. One of these groups is agro-polymers, i.e. those derived from
biomass. The other consists of bio polyesters, which are those derived
from microorganisms or synthetically made from either naturally or
synthetic monomers [16].
together again through condensation reactions to form peptide bonds, which are
consisting of amide functional groups. Examples of bio polyesters
includes polyhydroxybutyrate and polylactic acid [17].
SYNTHESIS
One of the most prevalent and most studied groups of biodegradable polymers
is polyesters. Polyesters can be synthesized in a number of ways comprising direct
condensation of alcohols and acids, ring opening polymerisation (ROP), and metal-
catalysed polymerization reactions. A big shortcoming of the step-wise
polymerization via condensation of an acid and an alcohol is the need to constantly
dehydrate this system in order to drive the equilibrium of the reaction forward. This
can lead to harsh reaction conditions and long reaction duration, resulting in a wide
dispersity. A large variety of starting materials can be used to synthesize polyesters,
and each monomer type endows the final polymer chain with diverse characteristics
and properties. The ROP of cyclic dimeric glycolic or lactic acid forms α-hydroxy
acids which then polymerize to form poly-(α-esters). A variety of organometallic
initiators can be applied to start the polymerization of polyesters, comprising tin, zinc,
and aluminium complexes. The most common is tin (II)octanoate and has been
accepted as a food additive by the U.S. FDA, but there are still some apprehensions
about using the tin catalysts in the synthesis of biodegradable polymers for biomedical
uses. The synthesis of poly (β-esters) and poly (γ-esters) can be carried out by
comparable ROP or condensation methods as with poly (γ-esters). Development of
metal-free process that comprises the use of bacterial or enzymatic catalysis in
polyester formation is also being researched upon [18]. These reactions have the
benefit of generally being regioselective and stereospecific but suffer drawback due to
the high expenses of bacteria and enzymes, long reaction times, and products of low
molecular weight.
Other than polysesters, other classes of polymers are also of interest. Polyanhydrides
are an dynamic area of research in drug delivery because they only degrade from the
surface and so are able to release the drug they carry at a constant
rate. Polyanhydrides can be made through a number of methods also used in the
synthesis of other polymers, comprising condensation, dehydrochlorination,
dehydrative coupling, and ROP. Polyurethanes and polyester amides are used in
biomaterials. Polyurethanes were initially exploited for their biocompatibility,
durability, resilience, but now being examined for their biodegradability.
Polyurethanes are normally synthesized using a diisocyanate, a diol, and a polymer
chain extender. The initial reaction is carried out between the diisocyanate and the
diol, with the diisocyanate in excess to ensure that the ends of the new polymer chain
are isocyanate groups. This polymer can then be treated with either a diol or a diamine
to form urethane or urethane-urea end groups, respectively. The choice of terminal
groups affects the properties of the resulting polymer. Moreover, the use of vegetable
oil and biomass in the formation of polyurethanes, as well as the conversion of
polyurethanes to polyols, is an active area of research [19].
METHODS OF BIODEGRADATION
The breakdown of polymer materials takes place by microbial action, photo
degradation, or chemical degradation. All three methods are categorized under
biodegradation, as the end products are stable and found in nature. Many biopolymers
can be dumped in landfills, composts, or soil. The materials will be broken down,
only if the required microorganisms are present. Normal soil bacteria and water are
normally sufficient, adding to the appeal of microbial reduced plastics [12]. Polymers
which are based on naturally grown materials such as starch or flax fibre are
vulnerable to degradation by microorganisms. The material may or may not
decompose more rapidly under aerobic conditions, subject to the formulation used,
and the microorganisms required. In the case of materials where starch is added as an
additive to a conventional plastic matrix, the polymer in contact with the soil and/or
water is attacked by the microorganisms. The microbes digest the starch, leaving
behind a porous, sponge like structure with a huge interfacial area, and lower
structural strength. When the starch constituent has been depleted, the polymer matrix
begins to get degraded by an enzymatic attack. Each reaction results in the scission of
184 Rummi Devi Saini
a molecule, gradually reducing the weight of the matrix until the whole of the material
has been digested. Another approach to microbial degradation of biopolymers
comprises growing of microorganisms for the specific purpose of digesting polymer
materials [13]. This is a more intensive process that eventually costs more, and avoids
the use of renewable resources as biopolymer feedstock. The microorganisms
required are designed to aim and breakdown petroleum based plastics. Although this
method reduces the amount of waste, it does not aid in the conservation of non-
renewable resources. Photodegradable polymers undergo degradation from the action
of sunlight. In many cases, polymers are attacked photo chemically, and broken down
to small pieces [14]. Further microbial degradation must occur later for true
biodegradation to be achieved. Polyolefin, a type of petroleum-based conventional
plastic, are the polymers found to be most vulnerable to photo degradation. Proposed
approach for further developing photodegradable biopolymers includes incorporating
additives which escalate photochemical reactions e.g. benzophenone, amending the
composition of the polymers to comprise more UV absorbing groups (e.g. carbonyl),
and synthesizing new polymers with light sensitive groups. An application for
biopolymers which experience both microbial and photo degradation is in the usage of
disposable mulches and crop frost covers. Some biodegradable polymer materials
experience a rapid dissolution when exposed to particular (chemical based) aqueous
solutions. As mentioned earlier, Environmental Polymer’s product ‘Depart’ is soluble
in hot water [15]. Once the polymer dissolves, the remaining solution consists of
polyvinyl alcohol and glycerol. Similar to many photodegradable plastics, total
biodegradation of the aqueous solution occurs later, through microbial digestion. The
necessary microorganisms are conveniently found in wastewater treatment plants.
Procter & Gamble has developed a product similar to Depart, named Nodax PBHB.
Nodax is alkaline digestible, which means that exposure to a solution with a high PH
causes a fast structural breakdown of the material. Biopolymer materials which
disintegrate on exposure to aqueous solutions are desirable for the disposal and
transport of biohazards and medical wastes. Industrial “washing machines” are
designed to dissolve and wash away the aqueous solutions to promote microbial
degradation.
the molecular weight of the polymer. Furthermore, the morphology of polymers also
greatly affects their rates of biodegradation. As enzymes mostly attack the amorphous
areas of a polymer hence the degree of crystallinity is also a key factor affecting
biodegradability. This is because the molecules in the amorphous part of polymer are
loosely packed so make it more prone to degradation. However, the crystalline part of
the polymer is more resistant than the amorphous region due to closer packing of the
molecules. The studies have shown that the rate of degradation of PLA decreases with
an increase in crystallinity of the polymer [21, 22]. The melting temperature (Tm) of
polymers also has a large effect on the enzymatic degradation of polymers. The higher
the melting point of the polymer, the lower is the biodegradation of the polymer [20,
23, 24].
Tm = ΔH/ΔS
where ΔH is the enthalpy change on melting and ΔS is the entropy change on melting.
The aliphatic polyesters [have ester bond (-CO-O-)] and polycarbonates [have
carbonate bond (-O-CO-O-)] are the two plastic polymers which show high
prospective to be used as biodegradable plastics, due to their susceptibilities to
lipolytic enzymes and microbial degradation. Whereas aliphatic polyurethane and
polyamides (nylon) are less prone to biodegradation as compared to aliphatic
polyesters and polycarbonates, as they have higher Tm values which results from their
large ΔH values due to the presence of hydrogen bonds among polymer chains
because of the presence of the urethane bond (-NH-CO-O-) and the amide bond (-NH-
CO-) in polyurethane and polyamides (nylon)respectively.
On the other hand, the high Tm and hence low biodegradablity of aromatic polyester
is caused by the small ΔS value due to increase in the rigidity of the polymer
molecule because of the presence of an aromatic ring.
Aliphatic Polyesters from Renewable Resources (Agro-Resources)
Polylactic Acid (PLA)
PLA, [-O(CH3)CHCO-]n Polylactic acid is a linear aliphatic polyester which is a
biodegradable and biocompatible thermoplastic that can be formed by fermentation
from renewable resources. It can also be synthesized by condensation polymerization
of lactic acid or from lactide by its ring opening polymerization in the presence of a
catalyst.
The production of PLA from lactic acid was established by Carothers in 1932 [36].
Lactic acid is also formed via starch fermentation, as a co-product of corn wet milling.
The ester linkages present in PLA are sensitive to chemical hydrolysis as well as
enzymatic chain cleavage. PLA is usually blended with starch to enhance its
biodegradability and decrease expenses. But, the starch-PLA blend has somewhat
brittleness which poses a major drawback in many of its applications. This limitation
can be overcome by using various low molecular weight plasticisers such as sorbitol,
glycerol and triethyl citrate. The PLA-degraders have not been found to be widely
186 Rummi Devi Saini
Poly(3-Hydroxybutyrate) (PHB)
PHB, [-O (CH3) CHCH2CO-]n is a natural polymer formed by several bacteria as a
resources to store carbon and energy. This polymer has attracted interest worldwide
because it can be produced from renewable low-cost feedstocks and the process of
polymerizations can be performed under mild conditions without causing much
impact on environment. Moreover, it undergoes biodegradation in both aerobic and
anaerobic conditions, without producing any toxic degradation products.
Several aerobic and anaerobic PHB-degrading microorganisms have been isolated
from soil such as Pseudomonas lemoigne, Aspergillus fumigatus, Comamonas sp.
Acidovorax faecalis and Variovorax paradoxus, from activated and anaerobic sludge
such as Alcaligenes faecalis, Illyobacter delafieldi, Pseudomonas, and from seawater
and lake water such as Comamonas testosterone, Pseudomonas stutzeri) [33,34]. The
percentage of PHB-degrading microorganisms in the environment has been found to
be 0.5-9.6% [10]. Majority of the PHB-degrading microorganisms has been found to
be capable of degrading PHB at ambient or moderate temperatures and only a few of
them are capable of degrading PHB at higher temperature.
Tokiwa et al. emphasized that as composting at high temperature is the most
promising technology for recycling biodegradable plastics so the thermophilic
microorganisms which can degrade polymers are significant in the composting
process [35]. A thermophilic Streptomyces sp. Isolated from soil can degrade PHB,
PES, PBS and poly [oligo (tetramethylene succinate)-co-(tetramethylene carbonate)] .
A thermotolerant Aspergillus sp. has been found to degrade 90% of PHB film after
five days cultivation at 50 °C [25].
Biodegradable Polymers 187
PCL can also be degraded by enzymes such as esterases and lipases [9]. The rate of
degradation of PCL depends on its molecular weight and degree of crystallinity.
Enzymatic degradation of PCL by Aspergillus flavus and Penicillium funiculosum
has been observed to be faster in the amorphous region [26]. The biodegradability of
PCL may be improved by copolymerization with aliphatic polyesters [27,28]because
copolymers have lower Tm and lower crystallinity as compared to homopolymers,
and hence are more prone to degradation. Tokiwa et al. [45] have studied the
hydrolysis of PCL and biodegradation by fungi. They have revealed that PCL can
easily be enzymatically degraded. The marine biodegradation of PCL has been
studied by Janik et. al. (1988) and they have reported that the PCL in seawater was
completely decomposed after eight weeks, whereas in salt solution it had lost only
20% of its weight. Hence it indicates that the enzymes in the seawater support to
speed up the biodegradation of PCL and other biodegradable plastics.
PCL is extensively used as a PVC solid plasticizer or as polyols for polyurethane
applications. It also finds some applications due to its biodegradable character in
provinces such as biomedicine, for example controlled release of drugs and clean
environment, for example soft compostable packaging material.
Polymer Blends
Blends of Polyester with Other Polymers
The biodegradable polymers are blended with other polymers in an approach to
reduce the overall cost of the material and modify the required properties and
degradation rates.
Blending is a much easier and rapid way to attain the desired properties relative to
copolymerization method.
Iwamoto et al. obtained blend plastics by mixing PCL with conventional plastics such
as low density polyethylene (LDPE), poly(ethyleneterephthalate) (PET),
polypropylene (PP), polystyrene (PS), PHB and nylon 6 (NY) and estimated their
enzymatic degradabilities. It was observed that the higher the miscibility of PCL and
conventional plastics, the tougher the degradation of PCL in their blends by R.
arrhizus lipase [46,47].
Various blends of PHB have been obtained with biodegradable and non-
biodegradable polymers and polysaccharides. The studies of enzymatic degradation of
these blends using PHB depolymerase from Alcaligenes feacalis T1 showed that the
weight loss of the blends reduced linearly with rise in the amount of PBA, PVAc or
PCL [47].
Koyama and Doi estimated the various properties and biodegradability of PHB/PLA
blend. It was observed that polymer blends having PHB generally showed improved
properties and biodegradability as compared to pure PHB [48].
CONCLUSION
The sectors of agriculture, automotives, medicine, and packaging all need
environment friendly plastics and polymers. Because the level of biodegradation may
be tailored to specific needs, each industry is able to generate its own ideal material.
The various modes of biodegradation are also a key advantage of such materials,
because disposal methods may be changed to industry specifications. Biodegradable
plastic is an innovative way of resolving the plastic disposal problem from the
viewpoint of development of new materials. Environmental responsibility is
constantly increasing in importance to both consumers and industry. For those who
yield biodegradable plastic materials, this is a key advantage. Biopolymers limit
carbon dioxide emissions during manufacture, and degrade to organic matter after
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disposal. Although synthetic plastics are a more economically feasible choice than
biodegradable ones, an augmented availability of biodegradable plastics will permit
many consumers to choose them on the basis of their environmentally responsible
disposal. The processes which hold the maximum potential for further improvement
of biopolymer materials are those which employ renewable resource feedstocks.
Biodegradable plastics containing starch and/or cellulose fibres appear to be the most
likely to experience persistent growth in usage. Microbial grown plastics are
scientifically sound, and a novel idea, but the infrastructure required to commercially
expand their use is still exorbitant, and difficult to develop. Time is of the essence for
biodegradable polymer development, as society’s current views on environmental
responsibility make this an ideal time for further growth of biopolymers.
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