H. Storz, K.-D.

Vorlop · Landbauforsch · Appl Agric Forestry Res · 4 2013 (63)321-332

DOI:10.3220/LBF_2013_321-332
321

Bio-based plastics: status, challenges

and trends

Henning Storz* and Klaus-Dieter Vorlop*

Abstract Zusammenfassung
The increasing concern about diminishing fossil resources Bio-basierte Kunststoffe: Status, Heraus-
and the impacts of the global warming is driving the growth forderungen und Trends
of the new bioeconomy. Bioplastics, thermoplastic biopoly-
mers that are either biodegradable or at least partly Die zunehmende Besorgnis über abnehmende fossile Res-
bio-based, are one of the fastest growing markets. The aver- sourcen und die Auswirkungen der Klimaerwärmung fördert
age growth rates over the past years have constantly been das Wachstum der Bioökonomie. Der Markt für Biokunststof-
double-digit. Though the production capacities are small, fe, thermoplastische Biopolymere, die entweder biologisch
currently approximately 0.5 % of the global plastics produc- abbaubar oder wenigstens teilweise bio-basierten Ursprungs
tions, recent market forecasts expect a sharp rise in the sind, ist einer der am schnellsten wachsenden. Obwohl die
upcoming three years. Due to identical property profiles and Produktionskapazitäten von Biokunststoffen gegenwärtig
established recycling processes, the largest growth is expect- noch klein sind, ca. 0,5 % der globalen Kunststoffproduktion,
ed for partly bio-based conventional plastics, especially for gehen aktuelle Marktprognosen von einem sprunghaften
bio-PET. Anstieg in den kommenden drei Jahren aus. Aufgrund iden-
This development was made possible by numerous inno- tischer Eigenschaften und etablierter Recyclingprozesse
vations in the fields of chemical catalysis, biotechnology, and wird das größte Wachstum für bio-basierte konventionelle
plastics engineering. It reflects an ongoing change in the Kunststoffe wie bio-PET erwartet.
bio-plastic industry, which increasingly focuses on the pro- Möglich wurde diese Entwicklung durch Innovationen in
duction of durable, bio-based plastics, after years of concen- den Bereichen der chemischen Katalyse, der Biotechnologie
tration on biodegradable plastics used for niche applica- und der Kunststofftechnik. Sie spiegelt einen andauernden
tions. But also the markets for bio-based and biodegradable Wandel der Kunststoffindustrie wider, die sich zunehmend
plastics are expected to continue their rapid growth. auf die Produktion nicht bio-abbaubarer Biokunststoffe kon-
This article reviews advances in production processes zentriert, nachdem der Fokus viele Jahre lang auf biologisch
and material properties of selected bio-based plastics. It abbaubaren Kunststoffen für Nischenanwendungen lag.
focuses on the most important bio-based plastics with estab- Aber auch für die Märkte der bio-abbaubaren Biokunststoffe
lished production and commercial applications. It further- wird erwartet, dass das schnelle Wachstum ahnält.
more provides an overview of new applications, and trends, Dieser Artikel gibt einen Überblick über ausgewählte bio-
as well as of major producers. basierte Kunststoffe mit Schwerpunkt auf Fortschritten in
den Bereichen Produktion und Materialeigenschaften. Er
Keywords: Bio-based plastics, biopolymers, renewable resour- konzentriert sich auf die wichtigsten bio-basierten Kunst-
ces, bioeconomy stoffe mit bereits etablierter Produktion und kommerziellen
Anwendungen. Darüber hinaus werden neue Anwendun-
gen, aktuelle Trends und wichtige Produzenten vorgestellt.

Schlüsselwörter: Bio-basierte Kunststoffe, Biopolymere, Nach-

wachsende Rohstoffe, Bioökonomie

* Johann Heinrich von Thünen Institute, Institute of Agricultural Technology,

Bundesallee 50, 38116 Braunschweig, Germany

Contact: henning.storz@ti.bund.de
322 H. Storz, K.-D. Vorlop · Landbauforsch · Appl Agric Forestry Res · 4 2013 (63)321-332

1 Introduction
Steadily growing since 1950, the worldwide production of
plastics materials has reached 288 million tons in 2012 (Plas-
tics Europe, 2013). Germany is one of the most important other plastics
PE
26 %
actors on the plastic markets and the biggest manufacturer 27 %
and processor of plastics in the EU. In 2012, the German
plastic industry produced 19.5 million tons of plastics and
generated a revenue of 25.1 billion euros (Plastics Europe
Deutschland, 2013). 11,860 kt
Large amounts of petroleum, approximately 7 % of the total
PUR
global production, are used for the production of plastics
6%
(Bozell, 2008). Consequently, today’s (renewable) energy
debate is also impacting the plastics industry. The challenges PET PP
17 %
are well known and essentially the same that underlie the 4%
energy debate. Namely fossil resources, especially petroleum PVC
PS
14 %
and gas, are of finite availability and have volatile and steadi- 6%
ly increasing prices. An additional pressure on decision
makers is generated by the growing political and public
Engineering plastics Commodity plastics
concern about the environmental impacts related with the
increasing utilization of plastics.
Although energy is the primary issue when it comes to
the impacts of the depletion of fossil resources, the size of
the challenge for the plastic industry is bigger than it might
other
seem. Unlike for the energy issue, there is only one renew- 26 %
able alternative for the production of plastics and bulk chem-
icals, and that is the use of biomass. The approach of using Packaging
biomass for the production of plastics is not a new one. The 35 %

production of the first modern artificial polymer, celluloid, 11,860 kt

total
and the vulcanization of rubber, were already sophisticated Electronic
and quite mature processes at the beginning of the last 6%
century. However, in the course of the petrochemical revolu-
tion, the markets for plastics based on renewable resources Automotive
have lost their importance to the petroleum based plastics 10 %
we are using today. Construction
23 %
Though the physical and functional diversity of plastics
seems enormous, 64 % of the processed volume is accounted
by five commodity plastics, namely polyethylene (PE), poly- Data Source: Consultic Marketing & Industrieberatung GmbH, 2012
propylene (PP), poly(vinylchloride) (PVC), poly(styrene) (PS),
and poly(ethylene terephthalate) (PET) (Figure 1). The Figure 1
remaining volume is accounted for by other engineering In Germany processed plastics 2011 – above: by type;
plastics like polyamides and polyurethanes and others. The below: by sector
largest share of the processed volume of plastics is used in
the packaging and construction sector, followed by automo-
tive and electronics applications. very diverse range of “bioplastics” which make it difficult to
Plastics have become an essential part of modern life and define general characteristics. For clarity here a basic defini-
offer great economic, ecologic, and social benefits: Examples tion: A bioplastic is a plastic material that is either bio-based
are functional packagings that reduce food spoilage, light- (partially or completely), biodegradable or features both
weight plastic components that lower the fuel consumption properties. The focus of this review is in bio-based plastics
of vehicles and aircrafts, and highly efficient insulation foams which are necessarily at least partly derived from renewable
that enable us to build zero-energy buildings. Except the lack resources but do not have to be biodegradable.
of renewability of their precursors there is nothing wrong The first bio-based products introduced to the markets
with the plastics we are using today. were poly(hydroxyalkanoate) produced by ICI (Great Britain)
Thus, changing the raw material base to bio-based feed- in the 1980s. Their development was driven by the increasing
stocks represents an appealing solution for many in the plas- demand for biodegradable plastics for packaging and agri-
tic industry. Accordingly, many companies have outlined the cultural applications. Due to high prices and the lack of
production of bio-based plastics as an objective in the past essential properties required for main applications, these
three decades. The result of the related research activities is a first products never penetrated important markets. However,
H. Storz, K.-D. Vorlop · Landbauforsch · Appl Agric Forestry Res · 4 2013 (63)321-332
323

the interest in bio-degradable products remained high and plastics including novel plastics, like thermoplastic starch
the number of applications rapidly grew beyond the and poly(lactic acid), as well bio-based versions of conven-
originally very limited number of simple packaging applica- tional plastics. The key selection criteria for the bio-based
tions. Biodegradable products with improved material prop- plastics discussed, are expected med-term production vol-
erties were developed in the 1990s. Some of these were umes and usage. Important progress in the development
completely petroleum-derived, which gave rise to some and diversification of material properties of novel bio-based
irritations among consumers. plastics is described and compared with the properties of the
In the late 1990s, the interest in bioplastics shifted conventional plastics they could substitute.
towards the use of renewable raw materials. In 2001, Nature-
Works LLC was the first company that produced a completely
bio-based plastic (poly(lactic acid)) in large quantities (USA, 2 Production of bio-based plastics
140 ktpa). Since then, the production of many bio-based
plastics has been demonstrated at pilot and demo scale. Bio-based plastics can be obtained via three principal routes
Some of the products are conventional plastics like PE and (Figure 2). The first approach is by modification of natural
PVC, others are partly bio-based (e.g. polyols, polyamides), polymers while preserving the polymer backbone (mainly)
and some of them are entirely new plastics such as poly(lac- intact. This is the most important approach today, used for
tic acid). Partly bio-based plastics often require petrochemi- the production of starch and cellulose-based plastics and for
cal monomers that cannot be resembled by bio-based various other bio-based polymers and fibers used in
replacements, at least not at a reasonable price. Today’s non-plastic and non-food applications.
bio-based plastics are sophisticated materials which could The second way comprises a two-step biomass conver-
technically be a substitute for around 90 % of the plastics we sion approach starting with the production of bio-based pre-
use today (Shen et al., 2010). cursors (monomers) by means of biochemical and/or chemi-
At present, however, high price levels and low produc- cal transformation followed by the polymerization of the
tion capacities of bio-based plastics prevent deeper market monomers in the final step (both steps are normally complex
penetration. According to a recent forecast, the production and can be divided in several sub-steps). If the monomers
capacities of bio-based plastics approximately correspond to obtained are bio-based versions of conventional monomers
0.5 % of the global plastic production (European Bioplastics, they are called drop-in (replacements). Conventional plastics
Institute for Bioplastics and Biocomposites, 2013; produced using drop-in monomers are advantgeous,
Plastics Europe, 2013). Though this is a rather small share, because they cannot be distinguished, neither structurally
numerous commercial successes and ongoing commercial- nor by performance, from their petrochemical counterparts.
izations impressively show the rapidly progressing change in Hence, they can readily enter existing processing and recy-
the plastic industry towards bio-based products. If this devel- cling systems. A good example is bio-based PE prepared
opment continues, bio-based plastics are likely to become an from bio-ethanol derived ethylene.
important pillar of the future bio-economy. Bio-based monomers that have new structures or have
This article reviews recent advances in the development, not been applied to the markets in the past are also used to
production, and application of a selection of bio-based produce plastics. These “novel” bio-based plastics often have

I. Modification of natural polymers

Natural polymers chemical Bio-based plastics

(e.g. starch, cellulose) modification (e.g. cellulose acetate)

II. 2-Step biomass conversation

chemical „Novel“ monomers

Biomass catalysis (e.g. lactide, FDCA) Bio-based plastics
((ligno-) cellulose, novel: PLA, PBS, PEF, PHA, ...
starch, sucrose) „Drop-in“ monomers drop-in: bio-PE, bio-PET, ...
bio-chemical
(e.g. ethylene, phthalic acid)
catalysis

III. Direct production in plants

photo- Bio-based plastics

CO2 + H2O
synthesis (e.g. PHA)

Figure 2
Principal routes to bio-based plastics
324 H. Storz, K.-D. Vorlop · Landbauforsch · Appl Agric Forestry Res · 4 2013 (63)321-332

different properties. Compared to the standard plastics they exhibit very different properties. Starch and cellulose
which they could replace, they often show an improved have in common that they cannot be processed as a thermo-
functionality and thus additional markets and applications. plastic material without prior modification.
However, in contrast to drop-in plastics, novel bio-based
plastics require the development and implementation of
new recycling systems. 2.1.1 Plastics from starch
This second approach to bio-based plastics is constantly Starch is a polysaccharide produced by green plants for the
gaining importance due to the advancements in the chemi- storage of energy. Due to its semi-crystalline structure, which
cal and bio-technological production of monomers. undergoes thermal degradation before the melting point is
The third route comprises the production of a polymeric reached, native starch cannot be applied to thermoplastic
material, which can be used as a plastic without further mod- processing.
ification, directly in microorganisms or plants. Because of the A bio-based plastic that is based on starch is thermoplas-
progress in genetic engineering and biotechnology which tic starch (TPS). It can be prepared from starch granules by
enables to move genes responsible for the production of a mixing and heating them in the presence of one or more
polymer like poly(hydroxyalkanoate) (PHA) from bacteria plasticizers, typically water and glycerol, in a process called
into crops, this route is becoming more feasible. However, as destructurization. TPS is an attractive bio-based material
favorable as direct production of bio-based plastics via pho- because starch is cheap, biodegradable, and abundantly
tosynthesis may seem, as complex are the related environ- available in large volumes. Furthermore, TPS is processable
mental and regulatory issues. Although this route has been with common equipment. However, TPS is very hydrophilic
intensively studied for many years now, no notable quanti- which renders it unsuitable for applications in humid envi-
ties of bio-based plastics have been produced accordingly. ronments (Liu et al., 2009). This currently limits the applicabil-
ity of TPS to niche products like fast dissolving dishwasher
tabs or adhesive tapes. Several solutions to improve the
2.1 Plastics from natural polymers properties of TPS were developed including the use of less
Polymers are very common in nature and used in many volatile and less water sensitive plasticizers like sorbitol or
industrial processes. By the annually produced volume, cellu- xylitol and the addition of suitable hydrophobic fillers like
lose, chitin, and lignin are most abundant. Currently, lignin lignin (Fang and Hanna, 2000; Kaewtatip and Thongmee,
and chitin have no notable commercial applications as 2013; Li and Huneault, 2011; Rahmat et al., 2009).
plastic materials, but their use as filler for rubber and thermo- Blending TPS and starch with hydrophobic plastics has
plastics and as prepolymers is being intensively studied extended their use as plasctic materials. The hydrophobic
(Chen et al., 2012; Doherty et al., 2011; Hatakeyama H and component prevents the direct uptake of water and
Hatakeyama T, 2010; Nandanwar et al., 2012; Srinivasa and increases the water resistance significantly. Via the variation
Tharanathan, 2007). of the plasticizer content the material properties can be
adjusted. Because most hydrophobic polymers are
incompatible with starch, the maximum starch content of
blends is limited to approximately 25 to 30 %. Higher
CH2OH CH2OH CH2OH
contents can be achieved by reactive blending in the
O O O
Cellulose OH OH OH presence of compatibilizers, which covalently link the
O O O components (Kalambur and Rizvi, 2006). Blends with
OH OH OH n conventional and bio-based polymers have been intensively
investigated (Nayak, 2010; van der Burgt et al., 1996; Willett
CH2OH CH2OH CH2OH
and Shogren, 2002).
O O O
OH OH OH Today, various commercial grades are available. Primarily,
O O O
these are polyester-based blends used for short-lived biode-
Starch OH OH
OH
O gradable products like bags, packaging films, agricultural
CH2OH CH2OH mulch films and protection foams. But also non-biodegrad-
O O O able starch-polyolefin blends have been commercialized.
OH OH OH
O O O Cereplast (USA) offers PE and PP TPS blends that are targeted
OH OH OH for long-term applications in automobiles, consumer-goods,
n
and construction. They offer significantly lower carbon foot-
Figure 3 prints than the pure polyolefins. Besides several companies
Structure of cellulose and starch with pilot/demo scale plants (< 10 ktpa) the most important
producers of starch plastics are Novamont (Italy, 120 ktpa)
and Rodenberg (Netherlands, 47 ktpa).
Among the natural polymers, only cellulose and starch are Though starch based plastics have developed a high
used for the industrial production of bio-based plastics. Their market penetration, the production capacities are not
production is in accordance with route I (Figure 2). Though expected to grow as fast as expected for other bio-based
their monomeric building blocks are very similar (Figure 3), plastics because many issues exist in using high amounts of
H. Storz, K.-D. Vorlop · Landbauforsch · Appl Agric Forestry Res · 4 2013 (63)321-332
325

starch (> 30 %) without compromising the material proper- 2.2.1 Poly(lactic acid)
ties, even in reactive blends. PLA plastics are amorphous or semi-crystalline polyesters,
that can be produced from the renewable fermentation
product lactic acid (LA). The LA molecule has an asymmetric
2.1.2 Plastics from cellulose carbon atom and therefore occurs in two forms. L-LA is pres-
Like starch, cellulose degrades prior to melting. But, because ent in many organisms. The enentiomer D-LA (mirror image
of a high degree of crystallinity, it is more stable than starch of L-LA), however, is very rare in nature (Chahal and Starr,
and cannot be dissolved or plasticized with common 2000). PLA can be prepared via direct condensation of LA or
solvents or plasticizers. For the production of a plastic mate- via ring opening polymerization (ROP) of the cyclic lactic acid
rial the cellulose, usually in the form of pulp, has to be chem- dimers, L,L-, D,D-, and D,L-lactide (Lim et al., 2008). The prod-
ically modified. The most important thermoplastic cellulose ucts of both routes are generally referred to as PLA (Figure 4).
material is cellulose acetate (CA) (Balser et al., 2000). Since it’s
first commercial production in the early 20th century, CA has
been an important plastic material, until it was replaced by HO O O O
-H2O
less expensive petrochemical plastics. CA is prepared by
acetylation of the hydroxyl groups of pulp with acetic anhy- OH O O
dride. Depending on the origin of the anhydride CA can be L-lactic acid L, L-Lactide
fully or partly bio-based.
-H2O
The thermal and mechanical properties and the bio-deg-
radation rate of CA, depend on the degree of acetylation
O
(Chandra and Rustgi, 1998). CA is predominantly used for fi-
O
ber applications (textiles and cigarette filters). Niche plastic- n
PLLA
applications include spectacle frames, handles and casings
of other high-value products, as well as polarized films, which Figure 4
are used for LCD displays. Synthesis of lactide and poly(lactic acid)
The industrial derivatization of pulp is a mature and
sophisticated process, which is performed under harsh
conditions. Recent research has focused on alternative According to a commonly adopted and more specific
solvents, such as ionic liquids (Gericke et al., 2012), the nomenclature, the polycondensation products of LA are
expensive recovery of these solvents remains the major called poly(lactic acid), and the products prepared by ROP of
drawback of these techniques. lactides are called polylactides.
Major producer of cellulosic polymers is Eastman Chemi- Besides being biodegradable, a major advantage of PLA
cal (USA), further producers are Innovia Films Ltd (UK), and is the possibility to process the plastic on common process
FKuR (Germany). Only a small share of the CA production equipment. The thermal and mechanical properties of PLA
(800 ktpa) is used for plastics applications. Due to the high properties depend on the ratio and the distribution of L- and
price and the niche character of most applications, a signifi- D-LA in the polymer chains.
cant change of the production capacities cannot be expect- Both, amorphous and semi crystalline PLAs, show a glass
ed in the close future. transition temperature (Tg) between 50 and 70 °C. Tg is an
important parameter. It is defined as the temperature above
which the amorphous regions of a plastic change from brittle
2.2 Bio-based polyesters to rubbery or liquid-like. Accordingly, native PLAs are brittle
Polyesters are one of the structurally and functionally most at room temperature. PLA solely consisting of L-LA blocks is
versatile groups of polymeric materials and formed when semi-crystalline due to the high structural regularity. The
dicarboxylic acids and di-functional alcohols or hydroxy acid crystalline regions (up to 37 %) provide additional mechani-
are polymerized. These monomers are quite abundant in cal strength, especially at elevated temperatures (Perego et
nature and can be produced via various fermentative al., 1996). The melting temperature of the crystals is typically
pathways, which were intensively studied and reviewed in around 180 °C (Lim et al., 2008). An important property of a
the last years (Bechthold et al., 2008; Gandini et al., 2009; van semi-crystalline thermoplastic is the rate at which it recrys-
Haveren et al., 2008). tallizes upon cooling from the melt. Fast and spontaneous
Depending on the utilized monomers and on the process crystallization is required for many plastic applications with
conditions, polyesters with a large spectrum of properties, short cycle times (e.g. injection molding). Pure PLLA crystal-
ranging from stiff to soft, can be prepared. An important lizes spontaneously, but the rate of crystallization decreases
feature of many polyesters is their ease of degradation due to with increasing D-LA content (Saeidlou et al., 2012). Less
the hydrolysis of the ester linkage, which is the reason for pure PLLA thus often contains a quasi-amorphous phase and
their biodegradability. Advances in biotechnology and overall shows inferior mechanical properties.
chemical catalysis have enabled the production of various In order to control the PLA crystallinity, several nucleat-
fully and partly bio-based polyesters. Currently the most ing agents have been investigated. Besides a variety of
important fully bio-based polyester is PLA. nanoparticles, talc and nano-clay have proven to be very
326 H. Storz, K.-D. Vorlop · Landbauforsch · Appl Agric Forestry Res · 4 2013 (63)321-332

good nucleating agents for PLA. Below 90 % L-LA content cally engineered plants according to route II or III (Figure 2)
PLLAs remain amorphous (Saeidlou et al., 2012). Because the (Braunegg et al., 1998). The generic chemical structure is
monomers L-LA and D-LA are enantiomers, PDLA plastics shown in Figure 5.
feature the same properties like the corresponding PLLAs. More than 150 different PHA monomers, hydroxyalka-
If both, L-LA and D-LA chain structures are present in a noic acids that differ in the length of spacer (X) and type of
PLA plastic, strong interactions between these complemen- side group (R), have been identified in PHAs (Steinbüchel and
tary structures can cause the formation of a very stable Valentin, 1995). PHA production using microorganisms
stereo complex. The effect is most pronounced in PLAs that comprises three basic steps (Suriyamongkol et al., 2007). The
contain equimolar amounts of L- and D-LA, e.g. in 1 : 1 blends fermentation step is usually a two-stage fed batch process,
of pure PLLA and PDLA (stereo complex PLA (scPLA)). which is followed by a solvent based extraction-precipitation
Compared to PLLA, scPLA shows a significantly higher step. After drying, the purified PHA plastic is ready for use.
melting temperature of 210 to 240 °C and spontaneous and The properties of PHAs strongly depend on their molecular
fast crystallization (Ikada et al., 1987). structure and composition. The simplest PHA, poly(3-hy-
Several scPLA production techniques have been devel- droxybutyrate) (P3HB) is very crystalline (up to 60 %) and
oped, including the application of chiral catalysts, melt and shows thermal and mechanical properties that can be com-
solvent blending (Auras et al., 2004; Ovitt and Coates, 2002). pares to PP and PE. However, they show a slow crystallization
Stereocomplex technology significantly improves PLA heat behavior and the elongation at break, a measure of the flexi-
stability and enables to replace PS and PP and other plastics bility, is two orders of magnitude lower compared to PP
in applications like hot beverage cups and microwave safe (Marchessault and Yu, 2005).
packaging. Besides crystallinity control, various plasticization
and processing techniques have been investigated in order
to overcome the inherent brittleness of PLA (Anderson et al.,
2008; Liu and Zhang, 2011). An often observed disadvantage R O O

was that improvements in either impact strength or the O (CH2)X O O

tensile modulus usually came along with reduction in modu- n m n
O
lus or tensile strength. PHA P(3HB-co-4HB)
New additives and processing technologies have expan-
ded the number of PLA applications, which today go well Figure 5
beyond the initial scope of biodegradable packagings. They Poly(hydroxyalkanoate) left: generic structure;
now include many durable applications like bottles, casings right: PHA-copolymer
of IT-products, cellular phones, films, and textiles (Jamshidian
et al., 2010). A bio-materials initiative launched by IBM is cur-
rently developing a PLA-ABS blend (30 % PLA) that could By using mixed cultures, genetically engineered organisms
replace polycarbonate/acrylonitrile butadiene styrene (PC/ and by varying the carbon sources used in the fermentation
ABS), the predominantly used plastic material in IT-products. process, the final product properties of PHAs can be tailored
The remaining technical challenge is to achieve adequate (Madison and Huisman, 1999). Important progress has been
flame retardancy. made in fine-tuning the properties of PHA-copolymers com-
Several companies in Belgium, China, Japan, Switzerland, prised of 3-hydroxybutyrate and 3-hydroxyvalerate or 3-hy-
and the Netherlands have installed small PLA productions droxyhexanoate and 4-hydroxybutyrate. They are more flexi-
capacities (several ktpa). NatureWorks LLC remains the ble than P3HB and can be adjusted to match the property
world’s only large-scale commercial producer of PLA (USA, profile of commodity plastics like PP, PE and PET (Laycock et
140 ktpa). However, the Dutch lactide producer Purac, is al., 2013; Marchessault and Yu, 2005).
providing Lactides (Thailand, 75 ktpa) for PLA production, Meredian PHA is currently operating and expanding the
has started up the world’s first D, D-lactide production in world’s largest plant (USA, 15 ktpa, 30 ktpa by 2014). Several
2009 (Spain, 5 ktpa). It is currently used in the production of commercial PHA grades, optimized for a broad range of
heat resistant scPLA foam which could be a biodegradeable applications, including injection molded items, films, foams,
substitute for expandable polystyrene. Though PLA prices and fibers, are currently available. According to the manufac-
have significantly fallen in the last years, they are still not turers, PHA production capacities are currently about 35 ktpa.
competitive with commodity plastics. NatureWorks LLC At the current stage of commercialization, the produced
assumes to reach cost parity with PET and PS due to an grades are mainly used for product development. A project
increased economy of scale by 2015. that could have an important impact on the demand for PHAs
is a replacement for PC/ABS (50 % PHA) in housings, also in-
vestigated by the aforementioned bio-materials initiative.
2.2.2 Poly(hydroxyalkanoate) However, PHA are still among the most expensive bio-
PHAs are a group of naturally occurring, amorphous or semi based plastics. An important cost driver is the energy inten-
crystalline polyesters, that are biocompatible and fully sive extraction and purification step, which adversely is also
biodegradeable (Chen, 2010). PHAs can be produced via in contradiction with the principles of green chemistry
bacterial fermentation of renewable feedstocks or in geneti- (Koller et al., 2005)
H. Storz, K.-D. Vorlop · Landbauforsch · Appl Agric Forestry Res · 4 2013 (63)321-332
327

2.2.3 Poly(butylene succinate)

Poly(butylene succinate) (PBS) (Figure 6) is a semi-crystalline, 41 % 59 %
non-biodegradable, biodegradable,
completely biodegradable polyester that is produced by bio-based fossil and bio-based
polycondensation of succinic acid and 1,4-butanediol (BDO)
(Xu and Guo, 2010).
725 kt
total capacity

O O

2010
HO (CH2)4 OH HO (CH2)2 OH
butanediol succinic acid 28 %
-H2O
15 % 16 %
12 % 12 %
O O 7% 8%
2%
O (CH2)4 O (CH2)2
n

Figure 6 58 % 42 %
non-biodegradable, biodegradable,
Synthesis of poly(butylene succinate) bio-based fossil and bio-based

Today, PBS is produced in various demo and pilot plants, 1,161 kt

mainly from petroleum based monomers. The current total capacity
production capacity is comparatively low (<  20 ktpa). How-
ever, bio-based routes to succinic acid and BDO have been
2011

extensively investigated (Cheng et al., 2012; Song and Lee, 39 %

2006). Several processes have been developed, including the

fermentation of carbohydrates using various types of bacte-
ria and fungi. A straight forward route to bio-based BDO is by 17 % 16 %
fermentation of sugars using genetically modified microbes 10 % 11 %
(Yim et al., 2011), demonstarted on a pilot-scale by Genomat- 2% 2%
3%
ica, or via the catalytical hydrogenation of bio-succinic acid
(Cukalovic and Stevens, 2008; van Dien, 2013).
PBS is a white thermoplastic material with a low Tg of 84 % 16 %
-45 to -10 °C and a melting point of 90 to 120 °C. It generally non-biodegradable, biodegradable,
bio-based fossil and bio-based
features good mechanical properties, similar to those of PE
80 %
and PP (Hwang et al., 2012). Some flexural and barrier proper-
ties, however, are not favorable for some applications (Ray and
Okamoto, 2003). In order to adjust these properties PBS is usu- 6,185 kt*
ally blended with other thermoplastics, e.g. TPS or PLA, or total capacity
comonomers like terephthalic acid or adipic acid are
incorporated (Xu and Guo, 2010). The addition of nanofillers
2017

like clays or carbon nanotubes has also shown to be an effi-

cient way to improve the material properties (Yang et al.,
2007). Since the first commercialization in 1994 further PBS
grades, homopolymer, copolymer, and blends with other bio- *estimated
based plastics, have been commercialized. They can be easily
4% 7%
processed with conventional polyolefin equipment. Main 3% 4% 3% 2%
1%
applications include packaging films and foams, agricultural
mulch films, disposable goods, and fibers (Xu and Guo, 2010). er -PE T A ste
rs nd
s
PH
A er
oth bio -PE PL
lye ble oth
Due to a lack of availability of bio-based succinic acid and bio Po rc h
Sta
BDO in larger volumes, PBS is currently mainly based on fossil
Data Source: European Bioplastics 2012, IfBB 2011,2012,2013
resources. However, the bio-based content is expected to Figure 7
increase, because the production capacities of the constitu- Global production capacity of bioplastics in 2010, 2011 and 2017
ent bio-based monomers are, according to announcements
of several companies and joint ventures (Myriant, Reverdia,
Bioamber and BASF, CSM Purac and Genomatica), about to ships is a 100 % bio-based PBS for large volume durable mar-
be expanded. The shared objective of these working partner- kets such as in the automotive interior parts.
328 H. Storz, K.-D. Vorlop · Landbauforsch · Appl Agric Forestry Res · 4 2013 (63)321-332

2.3 Bio-based conventional plastics availability of the raw materials are the key criterions for
The initial focus of bioplastics was on applications that siting a bio-PE plant.
required biodegradability. Accordingly, the production Braskem, the first producer of bio-PE, has built its large
capacities for durable bio-based plastics have remained scale production facility (200 ktpa) in Triunfo (Brazil). It utiliz-
comparatively low. However, most of the ‘commodity’ appli- es sugar cane ethanol and started production in late 2010.
cations of plastics do not require fast degradability but a The produced PE grades target applications in packaging
bio-based origin is increasingly request­ed. Recent market (food and cosmetics), toys, and automotive parts. Against the
studies show that the plastic industry responds to the expectations of many, the first production was sold out very
increased demand with shifting the production towards fast, although bio-PE was priced at a premium of about 50 %
bio-based conventional plastics that are not biodegrad- compared to conventional PE. Packaging converter Tetra Pak
able. Besides the expected rapid increase of the total recently, announced plans to use bio-PE for the production
production capacities to about 6.185 ktpa by 2017, Figure 7 of its packaging material factories in Brazil. This initial test
shows the shift of the largest segment from biodegradable would increase the renewable content of about 13 billion
plastics (59 % in 2010) towards bio-based non-biodegrad- packages annually produced in Brazil to up to 82 %.
able plastics (84 % by 2017) (Data sources: European
Bioplastics, Institute for Bioplastics and Biocomposites,
2013; European Bioplastics, Institute for Bioplastics and H CI
Biocomposites, 2012; European Bioplastics and University Bio-vinylchloride Bio-PVC
of Applied Sciences and Arts, 2011). Since 2011, the most CI H H n
important bio-based non-biodegradable plastic has been H
bio-PET, which is expected to grow at an exceptional rate Bio-PE
HO Bio-ethylene
due to the increasing demand for bio-based bottles, and Bio-ethanol H n
bio-PE. However, though not at the same ratelike the drop-
in plastics,also the novel biode­gradable plastics PLA and O HO
OH
PHA are also expected to grow significantly (nova-Institute Bio-ethyleneoxide Bio-ethylene glycol
GmbH, 2013; European Bioplastics, Institute for Bioplastics
and Biocomposites, 2012).
Figure 8
Conversion of ethanol to polyethylene, polyvinylchloride
2.3.1 Bio-based polyethylene and ethylene glycol
By the annual production volume, PE is the most important
conventional plastic material. It is extensively used in a wide
range of applications especially packaging and construction. 2.3.2 Bio-poly(ethylene terephthalate)
Conventional PE is produced by radical polymerization of the PET is a thermoplastic polyester produced by polycondensa-
petrochemically produced monomer ethylene. Alternatively, tion of ethylene glycol (EG) and terephthalic acid (TPA). It is
bio-based ethylene can be prepared from ethanol. This one of the most employed plastics and predominantly used
allows the production of bio-based PE using existing polym- in fiber (textiles) and packaging (bottles and food containers)
erization recators. applications. PET production comprises two steps. The first of
Figure 8 shows the reaction scheme of the drop-in these is esterification of TPA with EG, the second is polycon-
approach, which corresponds to route II (Figure 2), starting densation, in which PET is formed via a transesterification
with the dehydration of ethanol to ethylene and followed by reaction. High-viscosity PET grades used for bottles or tech-
conventional polymerization to PE (Bedia et al., 2011). Via the nical yarns are typically produced by chain extension in an
derivatization of bio-based ethylene, further important additional process step (Rieckmann and Völker, 2004). EG
bio-based monomers can be obtained (van Haveren et al., and TPA are typically sourced from petroleum but can alter-
2008). Examples shown are vinylchloride, the precursor of natively be produced via bio-based routes.
PVC and ethylene glycol, a monomer for used in the produc- Conventionally, EG is produced via the hydrolysis of
tion of bio-PET. ethylene oxide, a product of the catalytical oxidation of
Technically, the depicted routes are not essentially new. ethylene (Figure 8). Provided bio-based ethylene is available,
The bio-based production of plastics and other chemicals the production of bio-EG is straight forward and can be done
had been common processes in Brazil and India in the 1960s in existing plants. As India Glycols demonstrates with its
and 1970s (World Bank, 1980). For as long as the price for production of bio-EG and other bio-glycols since 1989
petroleum was low, the production discontinued and the (175 ktpa) this route can be technically and economically
technology stayed economically unattractive. With the rising feasible. The production of bio-based TPA is not as simple.
price level however, the technology has regained interest Many processes have been developed and demonstrated at
and many old processes have been reinvestigated recently small scale, but none has reached a larger, commercial scale
(Morschbacker, 2009). (Dodds and Humphreys, 2013). One of the most advanced
The raw material costs represent the most important processes uses bio-based isobutanol. The related production
part of the production costs of bio-PE. Hence, price and scheme, depicted in Figure 9, starts with the biotechnological
H. Storz, K.-D. Vorlop · Landbauforsch · Appl Agric Forestry Res · 4 2013 (63)321-332
329

production of isobutanol which is subsequently transformed ioxide and water barrier properties PEF might even outper-
via isobutylene and paraxylene into bio-TPA via form PET which could reduce food spoilage due to shelf life
multiple catalytical conversion steps. extension (van Es, 2013). Dutch company Avantium cur-
The bio-PET used today is partly bio-based, made of rently operates a FDCA pilot plant (40 tpa) and announced
bio-based EG and petroleum-derived TPA. Bio-PET has an plans to build a commercial-scale plant (40-50 ktpa) by
bio-based carbon content of 20 %. In 2011, the production 2015.
capacity for bio-based PET reached 620 kt, a 12-fold capacity
increase compared to 2010 (Figure 7). Trigger for this sudden
and unexpected increase was the great success of the Plant- 3 Challenges and trends
Bottle, a beverage bottle made of bio-PET, which was intro-
duced by Coca Cola in 2009. Meanwhile other large food Since the introduction of the first modern bio-based plastics
manufacturers use the PlantBottle for their products and some 30 years ago, the sector is developing very dynamical-
competitor Pepsi announced to introduce the first fully ly. Due to the rising price of petroleum and rapid technolog-
bio-based bottle, however yet provided only lab-samples of ical advancement, the initially very high price level was
the new bottle. lowered significantly. However, todays bio-based plastics still
With the expressed goal of Coca Cola to switch to a fully remain too expensive to compete with conventional plastics.
bio-based bottle by 2020, the bio-PET production capacities Though, the most important challenge that has to be
are expected to reach 5.000 ktpa by 2016 and to further addressed in the coming years is the further reduction of the
increase by 2020, (European Bioplastics, Institute for Bioplas- production costs. Economies of scale effects are most
tics and Biocomposites, 2012; nova-Institute GmbH, 2013). To important to enable competitive price levels. However,
achieve this goal, Coca Cola cooperates with several renew- because the supply-chains for bio-based products are typi-
able chemicals companies and bio-EG plants are being built, cally quite long, their up-scaling is challenging, especially
e.g. in Taiwan (Greencol, 175 ktpa) or are in planning in Brazil because many of the required technologies have not been
(JBF Industries, 500 ktpa). tested before.
The commitment stimulated the development of a bio- The feedstock selection will be the most important chal-
based replacement for PET, poly(ethylenefuranoate) (PEF). It lenge for three reasons: (1) substrate costs typically account
can be prepared from EG and 2,5-furandicarboxylic acid for 40-60 % of the total costs of bio-based products (Demain,
(FDCA), a dicarboxylic acid that is structurally comparable 2007). (2) the overall yield of the production of bio-based
with PET. FDCA can be produced from renewable resources. monomers is usually significantly lower than the production
The process, also shown in Figure 9, starts with the conver- of similar petrol based monomers. (3) The simple scale up of
sion of carbohydrates to hydroxymethlyfurfural (HMF). the current bio-based plastics production technologies,
Adjacent catalytical oxidations yield FDCA (Bozell and these usually utilize first-generation feedstocks like sugar
Petersen, 2010). The last step to PEF is a classical polyesterifi- cane or corn, are likely to increases the competition of the
cation of FDCA and EG. Because FDCA and TPA have related production of food and bio-based chemicals.
structures, bio-based TPA can be prepared from FDCA. The In order to avoid unsustainable demand, research is currently
missing two carbon atoms in FDCA can be supplied by focusing on lignocellulosic biomass and residue streams
bio-ethylene (Figure 9) (Eerhart et al., 2012). from agricultural and food production as feedstocks for bio-
This might, however, not be necessary because PEF and PET based chemicals (FitzPatrick et al., 2010). Although the devel-
compete in performance. Regarding the oxygen, carbon opment of these, so called second-generation technologies,

COOH O
HO O
OH O
HO (cat.) (cat.) (ox.) (cat.) bio-PET
(cat.)
COOH O
bio-TPA (drop-in)
(fermentation) n
Carbohydrates (cat.)

CH2OH CHO COOH

(cat.) HO O O
O OH O O
O O PEF
(ox.) (ox.) (cat.) O

O O COOH
n
H H
HMF FDCA

Figure 9
Conversion of sugar to bio-PET and PEF, a novel bio-based plastic that resembles the structure of PET
330 H. Storz, K.-D. Vorlop · Landbauforsch · Appl Agric Forestry Res · 4 2013 (63)321-332

is progressing, important issues, e.g. the development of effi- 4 Conclusions

cient lignocellulosic pretreatment, hydrolysis, and down-
stream technologies, have to be solved (Klein-Marcuschamer Societal demands for sustainable production and consump-
et al., 2010). In the meantime, large-scale production capaci- tion, and scientific research are leading to a fast commercial-
ties are increasingly installed in regions like South America ization of new applications for bio-based plastics. They are
and Asia where low-cost feedstocks, e.g. sugarcane and mo- begining to change the way plastics are produced. As a result
lasses are available in sufficient quantities. In parallel, new of the rapid pace of the developments, it is likely that
bio-based plastic products and marketing and image cam- bio-based plastics will be commonly found in commodity
paigns are launched. One of the best indirect results of this applications in the near future.
trend is the rise of green competition. Bio-PET is nice exam- The increasing number of customers that are willing to
ple for the game-changing impact big players can have on pay premium prices for green products, have become an
the development of technology, products and markets. important driver for this development. A recent study
Today’s bio-based plastics are predominantly bio-based showed, that product quality (97 %) and price (87 %) are still
versions of conventional plastics, mainly PET and PE. By 2016 influencing the buying behavior of EU citizen more than a
their share is expected to reach almost 90 %. This imbalance the impact of a product on the environment (84 %) (TNS
is not surprising because the utilization of drop-in replace- Political & Social network, 2013). While the gap between the
ments does not require any adjustments to existing polymer- impact of price and of the environmental impacts has
ization and processing equipment. Although drop-in decreased compared to earlier studies, the increasing
replacements are extending their lead, it remains difficult to number of companies that are going green with their
predict whether drop-in replacements or novel plastics will products might change this trend.
finally come out on top. The success of any approach will To permanently step out of their green niche, bio-based
depend on the final product cost. Bio-ethanol is currently the plastics have to be cost-competitive with their conventional
most versatile starting material for the production of counterparts. Given the current price differences of conven-
bio-based conventional plastic. However, because the tional and bio-based plastics and taking into account the
production of ethylene from sugar based ethanol comprises current supply situation with renewable resources, one can
decarboxylation and dehydration steps, the overall process is assume that bio-based and conventional plastics will be
not very efficient regarding the use of biomass. In contrast, used side by side in the forseeable future.
novel monomers can be produced with significant higher
atom efficiency. An example is the biotechnological produc- Glossary of Terms
tion of succinic acid in which carbon dioxide can be fixated BDO 1,4-Butanediol
rather than released as a byproduct (Cheng et al., 2012).
Although novel plastics like PLA and PHA can be EG Ethylene glycol
processed with standard processing equipment, replacing a FDCA 2,5-Furandicarboxylic acid
conventional plastic with a novel plastic is not a simple task. HMF Hydroxymethylfurfural
While the basic physical properties of novel plastics have
reached a high level of performance, incompatibilities with ktpa kilo tons per year
conventional additives often impair the property profiles. LA Lactic acid
Though an increasing number of additives are available for PBS Poly(butylene succinate)
novel plastics like PLA and PHA, the additives market for
bio-based plastics is small and still lacks solutions for import- PE Polyethylene
ant properties, e.g. the flame retardance. With the expected PEF Poly(ethylenefuranoate)
increase of novel plastic production volume, the market for PET Poly(ethylene terephthalate)
additive is likely to reach a volume that justifies the develop-
ment and production of new additives. PHA Poly(hydroxyalkanoate)
Novel plastics increasingly occur in existing recycling PLA Poly(lactic acid)
systems. Although novel plastics are recyclable and their
PP Polypropylene
separation technically feasible, existing recycling facilities
are not separating them out because they simply lack the PS Poly(styrene)
critical volume required for individual reclamation. The prob- PUR Polyurethane
lem that arises is that novel plastics are claimed to contami-
PVC Poly(vinylchloride)
nate and impair the performance of recycled conventional
plastics (Cornell, 2007; Soroudi and Jakubowicz, 2013). Be- ROP Ring opening polymerization
cause this could force waste management companies to re- Tg Glass transition Temperature
ject batches of otherwise recyclable material, it is increasing-
TPA Terephthalic acid
ly demanded to regulate the use of novel plastics, until the
required recycling capabilities are installed area-wide. TPS Thermoplastic starch
H. Storz, K.-D. Vorlop · Landbauforsch · Appl Agric Forestry Res · 4 2013 (63)321-332
331

FitzPatrick M, Champagne P, Cunningham MF, Whitney RA (2010) A biore-

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