Univerzita Tome Bati ve Zln

Tento studijn text vznikl v rmci een projektu FRV 357/2013

Inovace pedmtu polymery a ivotn prosted

Physical Properties Biodegradable Polymers

Ing. Adriana Gregorov , Ph.D.

1. Introduction

Polymers are natural or synthetic chemical materials with long, linear or branched chains
consisting of about 102 to 104 repeating monomer units. Polymers can be divided according to
various criteria such as their occurrence, composition of polymer molecules, polymerisation
types, physical properties, and chemical properties. With reference to the statistics, the EU27
countries with Norway and Switzerland produce about 65 million tonnes of plastics per year
and Czech Republic individually produces about 1.2 million tonnes of plastics. The leader in
plastics production in EU is Germany [1]. Worldwide consumption of polymers is expected to
reach 227 million tonnes by 2015 [2]. The majority of the plastic materials are not
biodegradable (Table 1) and not recyclable.

Table 1: Average decomposition time of some materials in the environment [adopted according 3]

Material Decomposition time

(year)
Glass Bottle 1 000 000
PET Bottle at least 450
Aluminium can 80-200
Leather 50
Nylon Fabric 30-40
Wool sock 1-5
Plywood 1-3
Newspaper 0.1

In Europe, the amount of plastic waste increases every year while landfilling covers about 10
million tonnes of plastic waste [4]. The main sector using plastics as well as producing post-
consumer waste is the packaging sector (see Figure 1). Considering these facts it is evident
that the increasing amount of plastic waste without acceptable solution might cause
environmental problems in the future. Besides landfilling, another way of utilization of the
waste such as recycling, material and energy recovery, and biodegradation (composting)
would be desirable.

a)

Automotiv
9% Electrical
electronics
Construction 7%
25% Household
3%
Furniture
4%

Agriculture
Packaging Others 3%
32% 15% Medicine
2%

b)

Construction Automotiv Electrical

9% 4% electronics
5% Household
3%
Agriculture
6%

Others
13%
Packaging
60%

Figure 1: Statistics from 2007 in Germany for a) consumption of plastics by various industrial sector and b) post-
consumer waste [1]

Since 1980s the ability of polymer products to degrade after their end of life can be named as
an important additional attribute. During last 30 years some new definitions and policies
related to the waste management have been incorporated in EU legislation. According to the
EU Commission, the priority of the EU Member States should cover the following hierarchy
(see Fig.2) [5].
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 Figure 2: Schema of the waste management hierarchy proposed by EU Commission in 2008 [5]

It was estimated that in the European Union in 2008 about 25 Mt of plastic waste was
generated and 48.7% out of this was land-filled. Nowadays the amount of short-lived plastic
products has increasing tendency while the majority of the plastic waste (e.g. plastic carrier
bags) is generated by packaging sector.
In March 2013 European Commission published review of current situation named Green
paper evaluating the constant increase of uncontrolled disposal of plastic waste and marine
litter in Europe as an alarmed situation. Consequently necessity of stronger waste policy was
indicated. One of the possible solutions is an implementation of biodegradable polymers in
the market. Additionally, the higher attention must be paid to differentiation between the
terms like degradable, compostable and biodegradable because their use is frequently
confused. Degradable plastics are materials undergoing irreversible chemical and/or physical
changes (e.g. thermally or by UV light) but it does not mean that they are biodegradable. In
case of biodegradable or compostable plastics, these materials should meet the special
requirements for biodegradability (ability of the material to decompose by the action of
naturally occurring microorganisms) or compostability (capacity of the materials to undergo
the decomposition through compositing). Particularly, the terms biodegradability and
compostability intersect each other. Furthermore, the clear operating conditions inevitable for
the successful biodegradation should be defined.
Compostable material should basically fulfil following attributes:
Biodegradability (EN 14046)
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 Disintegrability (EN 14045)
Absence of negative effects on the composting
Minimum concentration of heavy metals

Biodegradation can be accomplished by two different ways:

1) Aerobic biodegradation runs in the present of oxygen and produces carbon

dioxide, water, biomass, salts and minerals.
2) Anaerobic biodegradation starts without oxygen and produces methane, carbon
disulphide, carbon dioxide, water, biomass, salts and minerals.
As soon as all carbon (also in biomass) is converted to carbon dioxide, the biodegradation
process is finished. Between the most important factors influencing the speed of
biodegradation belong the value of molecular mass of polymer, the degree of crystallinity and
the geometric properties of the final product. Lower molecular mass and higher content of
amorphous fraction in the polymer accelerate biodegradation. Additionally, moisture and
temperature also contribute to easier biodegradation.
According to the definition, biodegradable or compostable plastics are materials in which the
degradation results from the action of microorganisms. The conversion of plastics into CO2,
methane and water and their biodegradability degree has to be measured by standardized tests.
Table 2 compiles the list of European standards concerning composting and biodegradation.
Further standardized methods testing biodegradation of plastics may be seen in the collection
of Eubeler et al. [6]. Certificates (see Figure 3) approving biodegradability/compostability of
polymer products are important for companies and society. For example the mark
Compostable Logo (being awarded since 1999 by the independent organisation - BPI -
Biodegradable Products Institute in New York, USA), or the mark DIN CERTCO (being
awarded by TV Rheinland, Germany.

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Figure 3: Compostable Logo awarded by BPI (USA) and DIN CERTCO awarded by TV Rheinland (Germany)
[7-8]

The compostable logo awarded by BPI means that materials (resins, bags, films, foodservice
products) fulfil criteria of ASTM D 6400 and/or ASTM D 6368 (USA norms for
compostability or biodegradability). The usual schedule for composting is time of 12 weeks
and temperature of 60C.

Table 2: European standards frequently used in the area of biodegradable polymers

Standard Title
Requirements for packaging recoverable through composting and biodegradation Test
EN 13432
scheme and evaluation criteria for the final acceptance of packaging
EN 14046 Packaging - Evaluation of the ultimate aerobic biodegradability and disintegration of
packaging materials under controlled composting conditions - Method by analysis of
released carbon dioxide
EN 14045 Packaging. Evaluation of the disintegration of packaging materials in practical oriented
tests under defined composting conditions
EN 14047 Packaging - Determination of the ultimate aerobic biodegradability of packaging materials
in an aqueous medium - Method by analysis of evolved carbon dioxide
EN ISO 14852 Determination of the ultimate aerobic biodegradability of plastic materials in an aqueous
medium - Method by analysis of evolved carbon dioxide
EN ISO 14855 Determination of the ultimate aerobic biodegradability of plastic materials under
controlled composting conditions. Method by analysis of evolved carbon dioxide. General
method
EN ISO 17556 Plastics - Determination of the ultimate aerobic biodegradability of plastic materials in
soil by measuring the oxygen demand in a respirometer or the amount of carbon dioxide
evolved
EN 14995 Plastics - Evaluation of compostability - Test scheme and specifications
EN 14806 Packaging - Preliminary evaluation of the disintegration of packaging materials under
simulated composting conditions in a laboratory scale test

Nowadays, 99% of plastic materials are made of petroleum-based resources; however the
indispensable fact that oil prices constantly grow and reserves of fossil fuels are limited,
material source changes should be considered by the future industrial development [9]. The
worldwide consumption of biodegradable plastics in 2012 was 269 000 tonnes while for
Europe, North America and Asia it was namely 55%, 29% and 16%, respectively [10]. The
above mentioned facts should lead research and market to increase their orientation to

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biodegradable and/or bio-based plastics (produced from renewable resources such as corn,
maize, rice, sugar cane or potatoes) as a potential alternative to standard petroleum-based
products [11].
Bio-based plastic can be either biodegradable or non-biodegradable and biodegradable
plastics can be naturally produced or derived from fossil fuel-based materials. Bio-based
plastics might be used in the future for a wide range of applications and it is actually the aim
of the research to modify their properties to make them more acceptable for industry and
society. Besides, environmental and waste legislation should support the elimination of plastic
waste landfilling and thus contribute to production of plastic products based on renewable
resources.
Renewability and/or biodegradability of plastic materials should be in modern society the
key request. Finally, green principles assessment or product life/waste cycle should also
quantify the impacts of bio-based (biodegradable or not biodegradable) plastics on the
environment (e.g. energy consumption, arisen emissions). Figure 4 shows an example of
plastic product acquisition-use-waste life cycle [12]. Life cycle assessment (LCA) has been
already standardized (ISO 14040). Surprisingly, according the work of Tabone et al. that
ranked some bio-based and petroleum-based polymers, poly(lactic acid) and poly(hydroxyl
alkanoates) received only the middle evaluation in the LCA while polyolefins were awarded
with the best ranking [13].
The aim of this chapter is to offer basic overview of biodegradable polymers that are
commercially available or exist under research, namely to describe their physical properties,
processing methods and applications in the market.

6
 Figure 4: Plastic product acquisition-use-waste life cycle adopted by Bohlmann [12]

2. Classification and physical properties of biodegradable

polymers

Biodegradable polymers can be classified according to their origin into three classes: naturally
produced renewable polymers, synthetic polymers derived from renewable resources and
synthetic polymers derived from petroleum-based resources. Some of the commercial
produced biodegradable polymers are shown in Table 3.
With reference to the statistics made in April 2013 by IHS Chemicals in Europe, the first
place in the market with biodegradable polymers belongs to starch based materials (62 %), the
second one to polylactides (24%) and the rest stay for other polymers (14%).

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 Table 3: The overview of the major biodegradable polymer suppliers

Polymer Trade name Company

Po(lylactic acid) (PLA) PLA-Natureworks Cargill, USA
Lacty Schimadzu, Japan
PLA Galactic, Belgium
L-PLA Purac, Netherland
PLA based resins: Bio-Flex, Biograde FKuR, Germany
PLA Cereplast
Polyhydroxyalkanoate (PHA) Biomer Biomer, Germany
Nodax Procter&Gamble, USA
Tirel Metabolix, USA
ENMAT TianAn Biologic Materials, China
Polycaprolactone (PCL) CAPA Perstorp, UK
Tone Dow chemicals, USA
Celgreen Daicel, Japan
Polyesteramide (PEA) BAK Bayer, Germany
Aliphatic polyesters (PBS) PBS Anqing Hexing Chemical Co,China
PBS BASF Germany
PBS Mitsubishi Gas Chemical, Japan
PBS Ire Chemicals, Korea
PBS Showa Highpolymer, Japan
Aliphatic copolyesters (PBSA) PBSA Bionolle Showa Highpolymer, Japan
EnPol, PBSA Ire Chemicals, Korea
PBSA Kingfa, China
PBSA IPC-CAS, China
Aromatic copolyesters (PBAT) Ecoflex BASF, Germany
Biomax Dupont (USA)
MATER-BI Novamont, Italy
Eastar Bio Eastman Chemicals, USA
Starch Solanyl Rodenburg, Netherlands

2.1 Naturally produced renewable polymers

Cellulose, lignin, starch, chitin, collagen, gelatin, hyaluronic acid, dextran, heparin, xanthan,
elastin, fibrin, pectin, and polyhydroxyalkanoates are biodegradable polymers naturally
occurring in plants or animals. In this subchapter starch and polyhydroxyalkanoates will be
introduced as representatives of biopolymers that are process-able with the common polymer
processing technologies.

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2.1.1 Starch

Starch is a mixture of linear amylose and branched amylopectin (see Figure 5) and belongs to
polysaccharides.

Figure 5: Structure of starch

Starch based polymer materials can be derived from various crops sources such as rice, corn,
potatoes, maize, wheat and cassava. Starch depending on the required properties can be
modified by various methods [14]:
a) Pre-gelatinization increase its water solubility
b) Degradation by enzymes decrease its viscosity
c) Chemical modification by esterification or etherification change its physical and
mechanical properties
d) Chemical crosslinking by change its physical and mechanical properties

Starch can be combined with other biodegradable polymers e.g. with polycaprolacton,
polyvinyl alcohol, polylactic acid with the aim to modify its properties. The company
Novamont (Italy) belongs to the biggest producers of starch based plastics e.g. Mater-Bi (with
different synthetic polymers). These resins have melting point of 120C and low crystallinity
about 4%. This material received the certification of its compostability and biodegradability
awarded by DIN CERTCO (Germany), CIC-Certiquality (Italy) and GreenPLA system
(Japan). MATER-BIR can be processed by thermoforming, injection moulding and extrusion
and is suitable for the production of bags, mulching films, disposable tableware, accessories
and packaging. The controlled composting test displayed in Fig. 6 shows that at least 85 % of
Mater-Bi material is compostable up to 120 days.

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Figure 6: Aerobic biodegradation under controlled composting conditions of cellulose and BATER-BI materials
(ISO 14855) [adopted by 15]

2.1.2 Polyhydroxyalkanoates (PHA)

Polyhydroxyalkanoates (Figure 7) are polyesters synthesised by a number of gram-positive

and gram-negative bacteria [16] and can be based on the number of carbon atoms divided into
three classes 1) short-chain length PHA with 3-5 carbon atoms, 2) medium-chain length PHA
with 6-14 carbon atoms and 3) long-chain length PHA with more than 14 carbon atoms [17].

Figure 7: The general structure of PHA, R= CH3 in the case of PHB

For living organisms, PHAs serve as intracellular storage materials for carbon and energy,
which are degraded at restricted availability of external carbon, thus providing the cell an
advantage for survival under starvation conditions. Poly(3-hydroxybutyrate) (PHB) is a
isotactic, thermoplastic homopolyester of 3-hydroxybutyrate and is the most investigated
compound among all PHAs. PHAs resins are commercial available with some potential for
the application in many industrial sectors [18-19]. The advantage of PHAs resin is their
renewability as well as their neutrality concerning CO2 production and biodegradability under
the compost conditions (within 2 months) [20]. However, their extensive applicability is

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limited by some drawbacks, for example high cost in the comparison to the traditional non-
biodegradable plastics; still an insufficient production mass; low temperature stability;
relatively slow crystallization and high brittleness [21-23]. Qualitative and economic requests
for a sustainability management of industries open various research areas, questions and
directions that should give the clear picture for the ways and means of biodegradable
polymers applications. Thermal and mechanical properties of PHB are shown in Table 4.

Table 4: Thermal and mechanical properties of commercial PHB

Properties PHB Source

Glass transition temperature (C) 18 [24]
Crystallization temperature (C) 70-80 [24]
Melting temperature in peak (C) 175-181 [24]
Vicat temperature (C) 147 [20]
Degradation temperature (C) 195 [20]
Ultimate tensile strength (MPa) 24-36 [20,24]
Youngs modulus (MPa) 1140-2900 [20,24]
Tensile strain (%) 2-9 [20,24]

PHB can be processed with standard techniques such as extrusion, injection moulding,
thermoforming, blown films.

2.2 Synthetic polymers derived from renewable resources

Biodegradation under the certain conditions with the controlled rated of degradation is an
additional attribute that may be reached by the synthesis of polymers containing for example
ester, amide or ether linkages in the backbone.

2.2.1 Poly(lactic acid) or Polylactide (PLA)

Poly(lactic acid) (PLA) is a semi-crystalline, thermoplastic, aliphatic polyester and its

monomer can be derived from annually renewable resources. Table 5 shows thermal and
mechanical properties of PLA.
PLA is one of the most important bio-based biodegradable thermoplastic polymers with
mechanical properties comparable to conventional petroleum-based plastics like
polypropylene and polyethylene terephthalate but with the low glass transition temperature.
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 Table 5: Thermal and mechanical properties of PLA

Properties PLA Source

Glass transition temperature (C) 40-64 [25-27]
Crystallization temperature (C) 106-120 [25-27]
Melting temperature in peak (C) 130-180 [25-28]
Heat distortion temperature (C) 55 [28]
Ultimate tensile strength (MPa) 45-66 [25-28]
Youngs modulus (MPa) 2600 [25-27]
Tensile strain (%) 2.5-30 [25-27]

The glass transition temperature value is an important attribute that influences rheological and
mechanical properties of PLA. The increase of the ambient temperature above Tg of PLA
causes the sharp loss of its stiffness. The Tg values of PLA are influenced by its molecular
weight, crystallinity, thermal history during processing, character of the side-chain groups,
tacticity of monomers and presence of additives in the composition.
Generally, as is described in Figure 8, PLA can be synthesized by four main ways. The
individual synthetic routes assign to PLA polymers different molecular weight: 1) the ring
opening polymerization (ROP with anionic, cationic and coordination-insertions mechanism)
possess to the obtained PLA molecular weight (Mw) above 100 000, 2) polylactides obtained
by the azeotropic condensation polymerization can reach Mw about 100 000 but the
necessity of solvents during polymerization is considered as the disadvantage, 3) PLA
obtained by the direct condensation polymerization can reach only low molecular weight
(Mw 1-30 000) 4) and PLA gained by the solid state polymerization usually reach relatively
low molecular weight up to 40 000.
Polylactides with low molecular weight are not suitable for the conventional polymer
processing such as extrusion or injection moulding.
Despite of the large variety of PLA grades on the trade mark, the applicability of PLA is still
limited by its severe brittleness, low heat distortion temperature, slow crystallization rate and
relatively high production costs.

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 Figure 8: The selected syntheses ways of PLA

Literature offers a number of research works devoted to the modification of PLA by

polymerization, copolymerization, blending and composite processing technologies. The
brittleness of PLA can be reduced through the incorporation of plasticizers; the toughness can
be improved by the application of impact modifiers and chain extenders. The crystallization
process can be supported by the presence of nucleation agents as well as by the processing
technology. The mechanical performance of resulted materials can be modified by the
addition of inorganic or organic fillers. The use of cheap fillers and the simplification of
processing technology help to decrease a price. However, the significant improvement of
thermal properties of polylactic acid is still a big challenge.
PLA is mostly used for packaging and textile industry, Figure 9 shows the PLA fiber
production route.

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 Figure 9: Example of PLA fiber production route [adopted according 29]

PLA can be degraded via hydrolysis, and the most effective microorganisms are lipase and
proteinase.

2.3 Synthetic polymers derived from petroleum-based resources

Generally, a broad range of synthetic polymers can be biodegradable under certain conditions
such as polyesters (aliphatic and aromatic), polyamides, polyurethanes, poly(amide-enamine)s
and polyanhydrides [30]. This sub-chapter introduces some important aliphatic and aromatic
polyesters and copolyesters.

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2.3.1 Aliphatic Polyesters

The monomer units are in polyester coupled by ester linkages and synthesised through
polycondensation with/without catalysts and ring-opening polymerisation with catalysts.

2.3.1.1 Poly(glycerol sebacate) (PGS)

PGS belongs to aliphatic synthetic biodegradable polyesters and can be synthesized by

polycondensation of glycerol and sebacic acid (Figure 10).

Figure 10: Polycondensation of poly(glycerol sebacate) [30]

The use of PGS is supposed in tissue engineering, drug delivery and in vivo sensing [31]. It
was declared that PGS is transparent, almost colourless, in vitro degradable, hydrophilic
thermoset, biocompatible in vitro and in vivo and can be processed by curing at 110-130C or
by solution casting e.g. in tetrahydrofuran, ethanol and isopropanol [30,32]. Thermal and
mechanical properties of PGS are shown in Table 5. PGS films have special viscoelastic
properties with shape memory (see Figure 11) [33].

Table 5: Thermal and mechanical propertis of poly(glycerol sebacate)

Properties PGS Source

Glass transition temperature (C) nd [30]
Crystallization temperature (C) -52.1 and -18.5 [30]
Melting temperature in peak (C) 5.2 and 37.6 [30]
Ultimate tensile strength (MPa) 0.2-0.5 [30,32]
Youngs modulus (MPa) 0.06 4 [30-32]
Tensile strain (%) 40-267 [30,32]
nd- not determined

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 Figure 11: Shape memory of PGS after 20 s, adopted according [33]

2.3.1.2 Poly(p-dioxanone) (PPDO)

PPDO is aliphatic synthetic biocompatible and biodegradable polyester synthetized by ring

opening polymerisation with various catalysts such as aluminium isopropoxide, stannous
octoate, zinc lactate or usingAl(OiPr)3-monosacharide initiator system (see Figure 12) [34-
35].

Figure 12: Ring opening polymerization of p-dioxanone using protected monosaccharide (1,2;3,4-di-O-
isopropylidene--D-galactopyranose)/Al(OiPr)3 initiator system

PPDO is semi-crystalline polymer with crystallinity about 30%. Bai et al. increased even
PPDOs crystallinity on 100% with the nucleation of 1 wt% calcium carbonate through
solution casting in the mixture of phenol/1,1,2,2-tetrachloroethane [36]. Thermal and
mechanical properties of neat PPDO are shown in Table 6.

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 Table 6: Thermal and mechanical propertis of Poly(p-dioxanone)
Properties PPDO Source
Glass transition temperature (C) -9.5 to -8 [37-38]
Crystallization temperature (C) 37 to 47 [37-38]
Melting temperature in peak (C) 107.7 to 133.8 [37-38]
Ultimate tensile strength (MPa) 27.2 [36]
Thermal stability (C) 268 [35,37]
Youngs modulus (MPa) nd
Tensile strain (%) 599 [36]
nd- not determined

The use of PPDO due to its biodegradability, bioadsorbility, biocompoatibility and high
flexibility was announced for the applications in tissue engineering, bone fracture fixation and
drug delivery. However, its high cost and fast degradation rate are disadvantages that hinder
its commercial use [38].

2.3.1.3 Polycaprolactone (PCL)

PCL is a semi-crystalline linear polymer with the crystallinity about 50%. It is synthesized
from -caprolactone via ring-opening polymerization in the presence of metal alkoxides (e.g.
tin octoate) (Figure 13).

Figure 13: Synthesis of polycaprolactone

PCL is biodegradable by some strains, yeasts and fungi within 1-2 years depending on its
molecular weight [39]. Its thermal and mechanical properties are shown in Table 7. PCL is
relatively cheap polymer process-able with the common techniques (e.g. extrusion) and is

17
hypothetically usable not only for packaging applications but also in tissue engineering due to
its non-toxicity [40-41].

Table 7: Thermal and mechanical properties of Polycaprolactone

Properties PCL Source
Glass transition temperature (C) -60 [42]
Melting temperature in peak (C) 60-65 [42]
Degradation temperature (C) 375 [41]
Ultimate tensile strength (MPa) 23 [42]
Youngs modulus (MPa) 160 [42]
Tensile strain (%) 700 [42]

2.3.1.4 Polyesteramides (PEAs)

PEAs are biodegradable polymers based on 1,6-hexanediol, -amino acid and diacid with 2-8
methylene groups. The main known polyeasteramide is referred as BAK 2195 (Bayer), based
on hexamethylene diamine, aidpic acid, butanediol and diethylene glycol (see fig. 14).

Figure 14: Chemical structure of BAK

This material is thermoprocess-able and its properties are comparable to low density
polyethylene (Table 8) but with triple higher price.

Table 8: Thermal and mechanical properties of BAK

Properties PE BAK Source

Melting temperature in peak (C) 115-125 [43]
Density (g/cm3) 1.16 [43]
Thermal stability (C) 442 [44]
Ultimate tensile strength (MPa) 21 [44]
Youngs modulus (MPa) 506 [44]
Tensile strain (%) 190 [44]

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However, PEAs have to be stabilized with antioxidant due to their thermo-sensitivity [43].
PEAs can be used as polymer matrices for drug delivery systems, hydrogels and
nanocomposites [44].

2.3.1.5 Poly(butylene succinate), (PBS)

PBS is synthetic commercially available biodegradable polymer belonging to the group of

poly(alkylene dicarboxylate)s. The synthesis of PBS is possible via polycondensation or
transesterification polycondensation of 1,4-butanediol and succininc acid as is shown in Fig.
15 [45]. PBS can be classified also to biodegradable polymers derived from renewable
materials because succinic acid can be obtained from the fermentation of microorganism on
glucose, starch and xylose [46].

Figure 15: Syntehsis of poly(butylene succinate) [45]

Its high sensitivity to hydrolysis enables its degradation to oligomeric or monomeric water
soluble products. PBS has an excellent processability and can be processed by the common
thermoplastic as well as textiles processing methods (extrusion, injection moulding, film
blowing and thermoforming). Physical properties of PBS (Table 9) enable its application as
agricultural mulching materials, packaging materials, and civil engineering materials.

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 Table 9: Thermal and mechanical properties of PBS

Properties PBS Source

Glass transition temperature (C) -32-38 [28,47]
Degree of crystallinity (%) 35-45 [28]
Melting temperature in peak (C) 115 [48]
3
Density (g/cm ) 1.26 [48]
Ultimate tensile strength (MPa) 33-40 [47-48]
Youngs modulus (MPa) 380-590 [47-48]
Tensile strain (%) 10-560 [28,47-48]

2.3.1.6 Poly(butylene adipate), (PBA)

PBA is a synthetic biodegradable, hydrolysable polymer and belongs to the polymer group of
poly(alkylene dicarboxylate)s. Fig. 16 shows its synthesis. PBA can be synthetized directly by
polycondensation or by transesterification polycondensation.

Figure 16: Syntehsis of poly(butylene adipate), (PBA)

PBA as polymer after polycondensation has low molecular weight; therefore it is used as an
additive with plasticizing effect for other polymers, for example polyvinylchloride [49].

2.3.2 Other synthetic biodegradable materials produced by copolymerization

Copolymerisation of polymers is an art of the synthesis that enables production of materials

with modified properties. For example, molecular weight and crystallinity are important
attributes influencing mechanical properties of polymers as well as their biodegradability.

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2.3.2.1 Poly(butylene succinate-co- adipate)s (PBSA)

PBSA is a high-molecular weight aliphatic biodegradable copolyester and can be obtained by

the transesterification of succinic acid, adipic acid and 1,4 butanediol in the presence of
Ti(OBu)4 catalyst [59]. The molecular structure of PBSA is shown in Fig. 17.

Figure 17: Structure of PBSA

PBSA may reach molecular of a several hundreds of thousands g/mol. This composition of
copolymer allows reducing the crystallization capacity and melting temperature (Table 10)
under the values exhibited by PBS and PBA polymers [50]. The processing of PBSA is not
complicated and comparable to polyolefins using the conventional melt mixing equipment.
Nikolic and Djonlagic [51] reported that due to lower crystallinity and higher polymer chain
flexibility PBSA is more susceptible to biodegradation than PBS.

Table 10: Thermal and mechanical properties of PBSA

Properties PBSA Source

Glass transition temperature (C) -40 [28,52]
Melting temperature in peak (C) 49-96 [28,53]
Heat distortion temperature (C) 69 [28]
Ultimate tensile strength (MPa) 19-20 [28,54]
Youngs modulus (MPa) 200 [54]
Tensile strain (%) 35-800 [28,57]

2.3.2.2 Poly(butylenes adipate-co-butylene terephthalate) (PBAT)

PBAT is a biodegradable aromatic copolyester that due to the copolymerization of adipic acid
and 1,4-butanediol with butylenes terephthalate exhibit higher glass transition temperature as
in the case of polymer - poly(butylenes terephthalate) (see Figure 18) [55].

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 Figure 18: The structure of PBAT

Thermal and mechanical properties and biodegradability of PBAT can be controlled by

adjusting of the molar ratio of monomers in the copolymer. Y. Someya et al. [56] reported
that the incorporation of Montmorillonite (layered silicate) in PBAT accelerate its degradation
during the burial in the soil. Table 11 shows physical properties of PBAT. One of the
commercial PBAT is BiomaxR 4026 that is hydro/biodegradable modified polyester resin, the
product of DuPont Company and Ecoflex F produced by BASF (Germany). Their
biodegradability was approved by BPI (Compostable Logo), DIN CERTCO (in Europe) and
Biodegradable Plastic Society in Japan. PBAT can be used as biodegradable resins with the
excellent thermal and mechanical properties in the area of food service packaging (films,
bowls, plates, cups, containers) as well as orthotics materials in medicine.

Table 11: Thermal and mechanical properties of PBAT

Properties PBAT Source

Glass transition temperature (C) 61 [57]
Crystallization temperature (C) 123 [57]
Melting temperature in peak (C) 110-120 [53]
Density (g/cm3) 1.25-1.27 [58]
Ultimate tensile strength (MPa) 10-36 [57-58]
Youngs modulus (MPa) 609 [57]
Tensile strain (%) 20-560 [57-58]

3. Conclusions

The major advantage of biodegradable polymers is their ability to degrade under special
conditions supported with the action of microorganisms and so ideally contributing to
reduction of plastic waste thrown in landfills. Enzymes play the role of catalysts for the
degradation but the hydrolysis is further predominant mechanism occurring mainly in
polyesters. Theoretically, the most polyesters are degradable by lipases, however, aliphatic-
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aromatic copolyesters with the content of aromatic co-monomer higher than 50% are mostly
inert against these enzymes [59]. Aliphatic and aromatic polyesters can be considered as the
largest group of biodegradable polymers with some physical properties comparable with non-
biodegradable polymers based on petrochemical chemicals.

The trademark offers only at narrow range of biodegradable polymers and materials; but their
production speedup depends mainly on their final price. Theoretically, higher use of
biodegradable materials in the industry and society might help to protect environment and
thus to contribute to sustainable economy. However, existing disadvantages, mainly higher
costs than those of the common non-biodegradable synthetic polymers (e.g. polyolefins)
decelerate wide utilization of biodegradable polymers. Nowadays, applications of
biodegradable polymers are announced mainly in field of packaging materials, engineered
fabrics, hygiene products, and agricultural films. Nevertheless the current research is also
focused on applications in medicine and pharmaceutical industry due to the higher acceptance
of initial costs in these areas. Current position of biodegradable polymers in the trademark
requests aiming modification of known biodegradable materials as well as investigation of
new types offer acceptable alternatives to common non-biodegradable polymers.

Acknowledgement
This work was created within the FRV project (grant No. 357/2013).

References
[1]. http://www.oecd.org/env/waste/46156805.pdf (accessed on 24/10/2013)
[2]. Plastic industry - statistics. http://www.cipet.gov.in/plastics_statics.html (accessed on
24/10/2013)
[3]. U.S. National Park Service; Mote Marine Laboratory, Sarasota, FL.,
http://www.mote.org/ (accessed on 24/10/2013)
[4]. http://www.plasticseurope.org/information-centre/press-room-1351/press-releases-
2013/european-plastics-industry-on-the-commissions-green-paper-on-plastic-waste-in-the-
environment.aspx (accessed on 24/10/2013)
[5]. Directive 2008/98/EC of the European Parliament and of the Council of 19 November
2008 on waste and repealing certain Directives
[6]. Eubeler J.P., Bernhard M., Zok S., Knepper T.P. (2009) Trends Anal Chem 28 (9),
1057-1072
23
[7]. http://www.bpiworld.org/products.html (accessed on 24/10/2013)
[8]. http://www.dincertco.de/en/index.html (accessed on 24/10/2013)
[9]. EUROPEN, 2011, Packaging and Packaging Waste Statistics in Europe: 1998-2008
[10]. www.chemweek.com, HIS chemical report, April 2012 (accessed on 24/10/2013)
[11]. Azapagic A., Emsley A., Hamerton I. (2003) Polymers: an Issue for Sustainability. In:
Polymers, the Environment and Sustainable Development. Ed. I. Hamerton, Publisher John
Wiley & Sons Ltd. England (2003), p. 5.
[12]. Bohlmann G.M. (2004) Environ Prog 23 (4), 342-346
[13]. Tabone M.D., Cregg J.J., Beckman E.J., Landis A.E.(2010) Environ Sci Technol 44
(21), 82648269
[14]. Whistler R.L., BeMiller J.N. (1999) Carbohydrate Chemistry for Food Scientists,
American Association of Cereal Chemists, St. Paul, MN
[15]. http://www.novamont.com (accessed on 24/10/2013)
[16]. Reddy C.S.K., Ghai R., Rashmi, Kalia V.C. (2003) BioresTechnol 87, 137-146
[17]. Volova T. (2004) Polyhydroxyalkanoates-Natural Polyesters of a New Generation, In:
Polyhydroxyalkanoates. Plastic Material of the 21st Century, Ed. T. Volova, Nova Science
Publishers, Inc. New York, 1-57
[18]. PHBV `OK` for use in food contact plastics. (posted 01.08.2008)
http://www.prw.com/subscriber/index.html (accessed on 24/10/2013), A Plastics News Global
Group site.
[19]. Laske S., Piontek M., Friesenbichler W., Wallner G., Achatz P., Burkhalter R.,
Langecker G.R. (3/2009) Biopolymer Paper for Laser Printing Applications in Proc. PPS-
25 Program & Abstracts, pp. 78, Personal Graphics & Advertiser Pvt. Ltd., Goa, Indien
[20]. Biomer, product sheet (Biomer P226 from the company Biomer, Germany) (accessed
on 24/10/2013)
[21]. Martin O., Avrous L. (2001) Polymer 42, 6209-6219
[22]. Huda M.S., Drzal L.T., Mohanty A.K., Misra M. (2006) Comp Sci Technol 66, 1813-
1824
[23]. Dacko P., Kowalczuk M., Janeczek H., Sobota M. (2006) Macrom Symp 239, 209-216
[24]. Gregorova A., Wimmer R., Hrabalova M., Koller M., Ters T., Mundigler N. (2009)
Holzforschung 63, 565-570
[25]. Gregorova A. (2013) Application of Differential Scanning Calorimetry tot he
Characterization of Biopolymers In: Appli cations of Calorimetry in a Wide Context-

24
Differential Scanning Calorimetry, Isothermal Titration Calorimetry and Microcalorimetry,
Ed. Elordy A.A., Intech Open Access Publisher ISBN 978-953-51-0947
[26]. Gregorova A., Hrabalova M., Wimmer R., Saake B., Altaner C (2009) J Appl Polym
Sci 114, 2616-2623
[27]. http://www.unicgroup.com/, NatureWorks PLA Polymer, Product sheets (accessed on
24/10/2013)
[28]. Xu J., Guo B.-H. (2010) Biotechnol J 5, 1149-1163
[29]. Ingeo, Technical Bulletin 70904, Basic Fiber Properties
http://www.natureworksllc.com/~/media/Technical_Resources/Fact_Sheets/Fibers/FactSheet_
Fiber_Yarn_BasicFiberProperties_pdf.pdf (accessed on 24/10/2013)
[30]. Wang Y., Ammer G.A., Sheppard B.J., Langer R. (2002) Nat Biotechnol 20, 602-606
[31]. Rai R., Tallawi M., Grigore A., Boccaccini A.R. (2012) Prog Polym Sci 37 (8), 1051-
1078
[32]. Chen Q-Z., Bismarck A., Hansen U., Junaid S., Tran M.Q., Harding S.E., Ali N.N.,
Boccacini A.R. (2008) Biomaterials 29, 47-57
[33]. Cai W., Liu C. (2008) Mater Lett 62, 2171-2173
[34]. Sugih A.K., Picchioni F., Heeres H.J. (2009) Eur Polym J 45, 155-164
[35]. Esteves L.M., Marquez L., Mller A.J. (2005) J Appl Polym Sci 97 (2), 659-665
[36]. Bai W., Chen D., Zhang Z., Li Q., Zhang D., Xiong C. (2009) J Biomed Mater Res
90(B) (2), 945-951
[37]. Hernandez-Montero N., Meaurio E., Elmiloudi K., Sarasua J.-R. (2012) Eur Polym J
48 (8), 1455-1465
[38]. Zhou Z.X., Wang X.L., Wang Y.Z., Yang K.K., Chen S.C., Wu G., Li J. (2006) Polym
Int 55 (4), 383-390
[39]. Tokiwa Y., Suzuki T. (1977) Nature, 270, 76
[40]. Hoque E., San W.Y., Wei F., Li S., Huang M-H., Vert M., Hutmacher D.W. (2009)
Tissue Eng 15(10), 1-12 (online article)
[41]. Patricio T., Gloria A., Bartolo P. (2013) Chem Eng Trans 32, 1645-1650
[42]. Vroman I., Tighzert L. (2009) Materials 2, 307-344
[43]. Zou Y., Wang L., Zhang H., Qian Z., Mou L., Wang J., Liu X. (2004) Polym Degrad
Stab 83, 87-92
[44]. Felton G.P. (2011) Chapter 4, In: Biodegradable polymers: Processing, Degradation
and Applications, Ed., G. P. Felton, Nova Science Publishers, Inc. ISBN:978-1-61209-534-9,
207-272

25
[45]. Tachibana Y., Masuda T., Funabashi M., Kunioka M. (2010) Biomacromolecules 11,
2760-2765
[46]. Song H., Lee S.Y. (2006) Enzym Microb Technol 39, 352-361
[47]. Makhatha M.E., Ray S.S., Hato J., Luyt A.S., Bousmina M. (2007), J Nanosci
Nanotech 8, 1-11
[48]. Phua Y.J., Chow W.S., Ishak Z.A.M. (2011) Express Polym Lett 5, 93-103
[49]. Ascione L., Ambrogi V., Pannico M., Carfagna C., Persico P. (2011) Funct Mat Lett 4,
361
[50]. Rizzarelli P, Puglisi C., Montaudo G. (2004) Polym Degrad Stab 85, 855-863
[51]. Nikolic M.S., Djonlagic J. (2001) Polym Degrad Stab 74, 263-370
[52]. Ray S.S., Bandyopadhyay J., Bousmina M. (2007) Polym Degrad Stab 92, 802-812
[53]. Pivsa-art S., Thumsorn S., Pavasupree S., O-Charoen H, Pivsa-Art W., Yamane H.,
Ohara H, (2013) Energ Proc 34, 563-571
[54]. Ray S.S., Bousmina M. (2006) J Polym Eng 62, 885-902
[55]. Gan Z., Kuwabara K., Yamamoto M., Abe H., Doi Y. (2004) Polym Degrad Stab, 83,
289-300
[56]. Someya Y., Kondo N., Shibata M. (2007) J Appl Polym Sci 106, 730-736
[57]. Gregorova A., Riedl E., Sedlarik V., Stelzer F. (2012) Asia Pac J Chem Eng 7 (S3),
S317-S323.
[58]. http://www.bioplastics.basf.com/pdf/Product%20information_Ecoflex_F_BlendC1200
_V1.pdf (accessed on 24/10/2013)
[59]. Mller R.-J., Kleeberg I., Deckwer V (2001) J Biotechnol 86, 87-95

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