Documentos de Académico
Documentos de Profesional
Documentos de Cultura
Maximilian Lackner
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Biobased Chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Biobased Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Lessons from First-Generation Biofuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Bioplastics or Biofuels? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Biopolymers and Climate Change Mitigation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Composite Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Abstract
Synthetic polymers are used extensively. Approx. 98 % of the 300 million tons
of polymers manufactured each year for packaging, construction, appliances,
and other technical goods are made from fossil sources, predominantly crude oil.
Combustion (thermal recycling) is a preferred route of disposal, at it removes
waste, however, CO2 emissions arise. Biobased polymers, by contrast, are made
from renewable resources. A second class of biopolymers for technical applica-
tions is biodegradable, being produced from conventional or renewable feed-
stock. Common biobased plastics are drop-in materials such as biobased PE,
biobased PP, and biobased PET, and frequently used biodegradable plastics are
PLA (polylactic acid), TPS (thermoplastic starch), and PHA (polyhydrox-
yalkanoates). Also, composites can contain natural fibers such as sisal or
hemp. Biobased polymer additives, e.g., plasticizers, are also in use. Renewable
M. Lackner (*)
Institute of Chemical Engineering, Vienna University of Technology, Vienna, Austria
e-mail: maximilian.lackner@tuwien.ac.at
feedstock reduces the carbon footprint of the plastics produced. Hence, bio-
polymers can contribute to climate change mitigation. Biodegradable bioplastics
avoid accumulation of the material in the environment, which has detrimental
effects, e.g., on marine wildlife. The degradation of bioplastics in general does
not release pollutants, and mineralization of the polymer yields CO2 and water in
case of hydrogen, carbon, and oxygen compounds. In this chapter, biobased
polymers, which have a substitution potential of up to 90 %, are briefly discussed
with respect to climate change mitigation.
Keywords
Biobased polymers Bioplastics PLA TPS PHA Bio-PP Bio-PE Bio-
PET
Introduction
Construction and building materials are produced on a large scale (Smil 2013),
having significant environmental impacts. According to the Cement Association of
Canada, the annual global production of concrete is approx. 3.8 billion m3. Steel
production also exceeds one billion tons/year. The annual plastic production, by
comparison, has reached 300 million tons. Approx. 4 % of the worlds oil produc-
tion is used for plastic production (Chen 2014), which by 2020, is estimated to reach
400 million tons (Biron 2014). Figure 1 shows the historic development of plastic
materials.
All these materials emit CO2 during their manufacturing and also during other
stages of their life cycles. The effect of plastics on the environment, however, is
mixed and diverse: at the end of their useful lifetime, which can be 100 years (e.g.,
for pipes) and a few minutes (e.g., for shopping bags), plastics can become a carbon
sink or release CO2 in waste incineration plants. Toxic gases can be emitted, too, in
case of uncontrolled combustion. Note that there are other issues, such as littering,
particularly in the marine environment, where microplastics cause harm. Such
effects are out of the scope of this chapter. During their useful life, plastics can
also save fuel, e.g., by less weight in cars and airplanes, hence showing a better life
cycle assessment (LCA) than other materials such as steel or aluminum. Cutting a
modern cars weight by 100 kg lowers fuel consumption by roughly 0.4 l/100 km
and reduces CO2 emissions by approx. 10 g/km (PlasticsEurope 2013). A weight
reduction of 5 % of the bodywork of a car through the use of plastics can yield an
average 3 % reduction in fuel consumption (PlasticsEurope 2014a). As a rule of
thumb, 1 kg of plastics in vehicles replaces 1.5 kg of conventional materials. In
Europe, for instance, the average emissions of all car models sold by one manu-
facturer in 1 year needs to drop from approx. 140 g CO2 per km (fleet average 2010)
to 95 g in 2020 and to 75 g (or possibly less) in 2025 and afterwards (McKinsey &
Company 2012).
Biopolymers 3
300
legislation
250
concerns for human health
production (Mr)
200
concerns for wildlife
150
accumulation in natural habitats
100
product/usage diversification
50
polymer invention and development biopolymers
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Fig. 1 Global plastic production with historical stages in the development, production, and use of
plastics and associated concerns and legislative measures (Source: European Commission 2011)
Biobased Chemicals
Today, most chemicals are based on fossil resources. Technically, biomass can
replace all fossil sources deployed for the production of materials and for generat-
ing low and medium temperature steam (Saygin et al. 2014). Cost-effective oppor-
tunities exist mainly for steam production from biomass residues and for
substitution of high-value petrochemicals such as plastics (Saygin et al. 2014).
Certain countries use coal (e.g., South Africa, Fischer-Tropsch synthesis) or natural
gas (e.g., United Arab Emirates for PE and PP production) instead of crude oil.
Biopolymers 5
352 Synthetic 13
Intermediates
rubber
44 Total organic
Biomass 20 Fibers
chemicals in
Oleochemicals Oxygen, nitrogen, use
7 chlorine 80 2717 Mt
Plastics 260
272
Processing
12 Net addition
Processing 163 Mt/year
Recycled waste 6
12 Post consumer
waste 136
35 95
Solvent, detergent &
surfactant loss 59
Incinerated Landfilled
Consumption of renewable raw materials for the chemical industry and for other markets,
2007 (in Mt/yr)
Current consumption of renewable raw materials
Surfactants
in the chemical industry
Lignin from 0
black liquor 113
7 Solvent
Bils & fats 140 Oleoch. 11
1
Sugar 169 Synthetic
4
Starch 60
Intermediates rubber
0.6
BioEtOH 55
4 Fibers
Cellulose 320
0
Consumption Proteins
in other Plastics
markets 113 4 107 17 55 316 ?
Fig. 3 World organic chemical industry mass balance and current consumption of the renewable
raw materials for the chemical industry and for other markets (2007). Net addition is the total
production of surfactants, solvents, synthetic rubber, fibers, and processed plastics minus the total
of postconsumer waste and material loss. Total quantities of starch and sucrose consumed for
bioethanol production are excluded (Source: Saygin et al. 2014)
Natural resources are also used to some extent, with Brazils bioethanol from
sugarcane being a prominent example. In Fig. 3 below, the global organic chemical
industrys mass balance and consumption of the renewable raw materials are shown
(2007 data):
According to a study by the US Department of Agriculture (USDA), the share of
biobased chemicals in the global chemical industry will rise from currently 2 % to
>22 % from 2008 (Philp et al. 2013a); see Fig. 4 below.
6 M. Lackner
Fig. 4 Trends in the production of biobased chemicals in relation to petrochemicals. (a) The
global growth of the biobased chemicals and polymers between 2001 and 2010, (b) US predictions
for growth of the biobased industry to 2025. All figures are in billion USD (Source: Philp
et al. 2013a)
Biobased polymers, which currently account for approx. 1.5 % of global plastic
production, are expected to gain significance in the coming years, as technology
improves, consumers demand more green products, and manufacturers want to
appear green, particularly in the area of plastics, which has a low environmental
reputation.
Biobased Polymers
Fig. 5 Typical applications of plastic materials in Europe (EU-27 + NO/CH) in 2013 (Source:
Alvarenga and Dewulf 2013)
Renewable
Based on renewable raw raw materials
Are biodegradable and
materials based on renewable raw
materials
Biopolymers Biopolymers
Conventional Biopolymers
polymers
e.g. PBAT, PBS,
Nearly all conventional PCL
plastics
e.g. PE, PP, PET
Are biodegradable
Petrochemical
raw materials
The most common biobased plastics are biobased PET, bio-PE, starch blends
and thermoplastic starch (TPS), polylactic acid (PLA) (Sin et al. 2013), and
polyhydroxyalkanoates (PHA) (Chen et al. 2011); see Fig. 7 below. PET consists
of 70 % terephthalic acid and 30 % monoethylene glycol (MEG). The latter can be
made from renewable ethanol, so a partly renewable drop-in polymer, which is
identical to petrochemically produced PET, is obtained. Such bio-PET can be
recycled normally. Research is ongoing for 100 % renewable PET (bottle) material.
The production capacity is approx. 2 % of current production volumes of
conventional plastics. Compound annual growth rates for bioplastics are signifi-
cantly above 10 % (PlasticsToday 2011; Globe Newswire 2013). The replacement
potential for biobased polymers is estimated between 33 % and 90 % (OECD 2011).
For a review on bioplastics, see, e.g., Lackner (2015), Ebnesajjad (2012), and
Niaounakis (2013).
Fig. 7 Global bioplastics production capacities in 2012 (left) and their use (right) (Source: European Bioplastics 2013)
9
10 M. Lackner
Fig. 8 The three circles of sustainability. Left, theory; middle, current status; right, change needed
for better balance (Source: Adams 2006)
Bioplastics or Biofuels?
Giving the limited quantity of high-value biomass available for either biofuel or
bioplastic production, e.g., in case of Brazilian ethanol from sugarcane, one might
ask the question which route is more environmentally sound. According to
Alvarenga and Dewulf (2013), deploying ethanol to produce biobased ethylene
(instead of fossil-based ethylene) for PE manufacturing would generate environ-
mental gains in the order of 32.0 MJ of fossil energy and 1.87 kg CO2eq, as opposed
to the use of ethanol for transportation (instead of gasoline), where environmental
gains in the order of 27.2 MJ of fossil energy and 1.82 kg CO2eq were estimated. It
was found that above a polymerization yield of 96 %, the bioplastics route was
better in terms of GHG emission reductions (Alvarenga and Dewulf 2013). CO2eq
stands for CO2 equivalent. It is that amount of CO2 which would cause the same
level of radiative forcing as a given type and amount of greenhouse gas (GHG).
Biopolymers 11
Fossil
Resource Polymerization
Use Disposal
Extraction & Manufacture
Fig. 9 Generic life cycle stages for polymers. The dashed line indicates a cradle-to-gate system
boundaries, the dotted line is an extension of that system boundary to cradle to grave, and the entire
figure is indicative of a cradle-to-cradle assessment (Source: Hottle et al. 2013)
Greenhouse gases (GHG) such as CO2, CH4 and N2O are emitted during feedstock
production, transportation, bioplastic manufacturing, packaging, distribution, use-
ful life, and at the end-of-life, which is considered in life cycle assessments (LCA).
In a typical LCA of bioplastics, the GHG from land use change (LUC, the so-called
carbon debt) for feedstock production is one of the most significant contributors to
the environmental impacts (Pei et al. 2011), e.g., in case of rainforest destruction for
plantations.
The system boundaries of LCA (the scope) may extend from cradle to gate,
cradle to grave, or cradle to cradle; see Fig. 9 below. The cradle-to-gate (dashed
lines) approach covers activities prior to usage, while cradle-to-grave approach
(dashed and dotted lines) includes the products use and end-of-life. Cradle to
cradle (whole chart) is also used. Sometimes, the scope cradle to pellet is assessed.
Life cycle assessment allows the comparison of like with like. A position
paper on LCA of bioplastics by industry association European Bioplastics can be
found in European Bioplastics (2008).
12 M. Lackner
10
Net GHG emissions (kg CO2 eq. / kg polymer)
4
3.2 3.4 3.4 3.4
2.7
2.1 2.3
2 1.9
2
0.3
0
PP
A6
A5
PE
S
S
G
E
s
6
PC
PP
am
p
B
66
su
ss
IP
PP
-P
PH
N
on
PL
PL
LD
o-
on
A/
H
O
T
C
2 0.7
yl
G
A/
Bi
PE
PL
BI
PE
PV
yl
N
PH
N
2.3 2.5
4
Fig. 10 GHG emissions in plastic production (From various sources: PLA/NG NatureWorks
PLA next generation, PLA5 NatureWorks PLA in 2005, PLA6 NatureWorks in 2006, PLA
polylactic acid, PVC sus PVC suspension, HIPS high impact polystyrene, PC polycarbonate,
GPPS general purpose polystyrene, PET am PET amorph, PET ssp PET solid-state polyconden-
sation, Bio-PP Braskem biobased polypropylene, Bio-PE Braskem biobased polyethylene
(Source: Philp et al. 2013b)
Guidelines for carrying out LCA are provided, e.g., by the International Orga-
nization for Standardization (ISO) 14040 series. Others were established by the US
Environmental Protection Agency (EPA) and the Society for Environmental Tox-
icology and Chemistry (SETAC), an international NPO (Hottle et al. 2013).
In Kim and Dale (2008), it was estimated that corn-derived PHB (polyhydrox-
ybutyrate, a potential replacement for PP) offers environmental advantages over
fossil polymers, with lower nonrenewable energy consumption (95 % reduction)
and lower greenhouse gas emissions (200 % reduction) compared to the petroleum-
based plastics.
Figure 10 below compares net GHG emissions, expressed in kg CO2eq per kg of
polymer, for conventional and biobased materials.
According to Tsiropoulos et al. (2014), a similar study, biobased polyethylene,
results in greenhouse gas emissions of around 0.75 kg CO2eq/kg polyethylene, i.e.,
1.4 times lower than petrochemical PE, yet more than the 2.5 kg CO2eq/kg found
by Philp et al. (2013b). Savings of nonrenewable energy use for bio-PE were found
to be roughly 65 % (Tsiropoulos et al. 2014). Such discrepancies in various studies
will be discussed below.
PHB, which belongs to the class of PHA, is a biodegradable biopolymer which
can be produced by bacteria and plants. Bio-PE and bio-PP are chemically identical
to PE and PP, since they share the same feedstock, only of different provenience.
They show significant CO2eq savings compared to their traditional counterparts.
Biopolymers 13
Yates and Barlow (2013) wrote that Biopolymers are generally considered an
eco-friendly alternative to petrochemical polymers due to the renewable feedstock
used to produce them and their biodegradability. However, the farming practices
used to grow these feedstocks often carry significant environmental burdens, and
the production energy can be higher than for petrochemical polymers.
They studied polylactic acid (PLA), polyhydroxyalkanoates (PHAs), and starch-
based polymers, with some of the results shown in Figs. 11 (PLA) and 12 (PHA).
The LCA studies focused on nonrenewable energy use (NREU) and global
warming potential (GWP). GWP is expressed in kg CO2eq per kg of polymer.
As Fig. 11 shows, several studies found that GWP levels of PLA production are
below those of competing conventional polymers, particularly in case of CO2
sequestration, while other studies found just the opposite. Carbon sequestration
stands for the long-term removal of CO2 from the system, e.g., by landfilling.
In case of PHA, there is also disagreement in the literature on whether the
biobased polymer has a lower GWP than its petrochemical counterparts. One
needs to acknowledge that biobased plastics have not yet reached the same level
of technological maturity as conventional plastics and that their currently smaller
manufacturing units cannot be as efficient as a few 100,000 t/year standard poly-
merization plants. The higher GWP results, e.g., from energy consumption during
production. Also, it needs to be highlighted that the outcome of life cycle assess-
ments depends on the system boundaries as shown below in Fig. 13.
End-of-life assessment is more comprehensive. However, it depends on the
chosen disposal route, which varies from country to country. For instance, in
Europe incineration is used more than in the United States, where landfilling
prevails, so other approaches such as cradle to pellet as mentioned above might
be more meaningful.
Composite Materials
Apart from biobased polymers, additives and fillers can also be biobased (Lackner
2015). An example of biobased PVC plasticizers are glucose esters (Yin
et al. 2014). Examples of compounds and composites with biobased fillers are
plastic wood composites (PWC), for which also recycled plastics can be used
(Najafi 2013). Biobased fibers for use in plastics (both conventional and biobased)
are, e.g., hemp fibers (Dhakal and Zhang 2015), cellulose fibers (Gonzlez-Snchez
et al. 2014), flax fibers (El-Sabbagh et al. 2014), sisal, kenaf, jute, and coir
(Wambua et al. 2003). Such fillers improve properties and can reduce both weight
and costs. For a review on bionanocomposites, see, e.g., (Reddy et al. 2013).
Composite materials with biobased ingredients and recycling of bioplastics
(Niaounakis 2013; Soroudi and Jakubowicz 2013) are not covered in this chapter.
It only has to be stated that recycling of bioplastics would require a separate
infrastructure, as some bioplastics are not compatible with regular recycling
schemes (e.g., PHB in PET will degrade properties strongly; (Lackner 2015)).
14 M. Lackner
Fig. 11 GWP and NREU for PLA studies and petrochemical polymers. Sequestration refers to
CO2 uptake by plants used as the feedstock. Ranges for petrochemical polymers cover values
reported in various comparative LCA studies and those provided by PlasticsEurope (Source: Yates
and Barlow 2013)
Biopolymers 15
Fig. 12 GWP and NREU for PHA studies and petrochemical polymers. Ranges for petrochem-
ical polymers cover values reported in various comparative LCA studies and those provided by
PlasticsEurope (Source: Yates and Barlow 2013)
16 M. Lackner
3.5
2.5
2.0
1.5
1.0
0.5
0.0
PHA PLA TPS
Fig. 13 Average global warming potential of biopolymers based on the extent of the system
boundaries of fifteen different LCAs. EOL end of life (Source: Hottle et al. 2013)
Discussion
From what was depicted above, bioplastics are a hot topic for researchers,
entrepreneurs, and customers/consumers alike, where the avoidance on crude oil
dependency is a main driver and climate change mitigation a welcome side effect.
Generally speaking, materials sell by properties (i.e., performance), not by price
(only). The costs of bioplastics are typically higher than those of conventional
polymers, which is partly due to more expensive feedstock and lack of economies
of scale. Since the main barrier to market penetration of bioplastics is their price
compared to that of oil-based plastics, a brief cost overview is shown here in
Table 2.
Biobased plastics will play a vital role in a bioeconomy (Philp et al. 2013c).
Some biobased plastics have a slightly higher density than petrochemical plastics
such as PE and PP, so when being used in transportation applications, they will not
result in the same fuel savings over the packagings or vehicles lifetime.
The IPCC writes in its Fourth Assessment Report (2007):
Table 2 Prices of bioplastics in 09/2012. Reference pellet prices (EUR per kg) PE = 1.58;
PP = 1.54; PET = 1.73 (Source: OECD 2014)
Product Company Location Capacity (tones) Price (EUR per kg)
PLA Nature Works United States 140,000 1.52.0
PLA Hisun China 5000 2.1
PHAs Metabolix United States 300/50,000 4.34.6
PHBV Tianan China 2000 4.14.3
Mater-Bi Novamont EU 75,000 3.45.1
Cereplast Cereplast United States 25,000 2.63.4
HDPE/LDPE/ Braskem Brazil 200,000 1.31.7
PP
Other DuPont Global 2000 2.56.9
Plantic
Innovia
Arkema, others
increased from 37 to 83 MtC per year over the past 40 years. Assuming a first order decay
rate of 10 to 20 % per year, this is estimated to be a global net annual removal of 3 to
7 MtCO2 from the atmosphere, which is negligible compared to other mitigation measures.
(IPCC Fourth Assessment Report: Climate Change 2007)
Conclusions
Bioplastics were shown in this chapter to offer the potential for reduced GHG
emissions compared to fossil plastics, rendering the same service level. Biopoly-
mers show some unfavorable results in several LCA studies; however, the imma-
ture nature of these technologies needs to be considered (future optimization and
efficiency improvements will come). Both drop-in replacements (e.g., biobased PE,
biobased PP, bio-PET) and novel bioplastics (e.g., PLA, TPS, PHA) can contribute
to climate change mitigation; however, a profound life cycle assessment including
potential land use change has to be carried out to have a clear picture about the net
effect. Further improvements in energy efficiency of feedstock production and
reduction of fossil fuel use in the process are needed.
Gerngross and Slater wrote that any manufacturing process, not just those for
plastics, would benefit from the use of renewable energy (Gerngross and Slater
2000), so it seems worthwhile to foster bioplastics from a climate change mitigation
perspective.
The second major advantage of bioplastics, which is not related to climate
change mitigation, is biodegradability as shown by some grades. Whereas the
lifetime of conventional plastic materials can be hundreds of years (Harvey
2012), biodegradable plastics are mineralized to CO2 and H2O. They generally do
18 M. Lackner
Outlook
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