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‘‘Plastics’’ were introduced approximately 100 years ago, and today are one of the
most used and most versatile materials. Yet society is fundamentally ambivalent
toward plastics, due to their environmental implications, so interest in bioplastics
has sparked.
According to the petrochemical market information provider ICIS, ‘‘The
emergence of bio-feedstocks and bio-based commodity polymers production, in
tandem with increasing oil prices, rising consumer consciousness and improving
economics, has ushered in a new and exciting era of bioplastics commercialization.
However, factors such as economic viability, product quality and scale of operation
will still play important roles in determining a bioplastic’s place on the commer-
cialization spectrum’’ (1).
The annual production of synthetic polymers (‘‘plastics’’), most of which are
derived from petrochemicals, exceeds 300 million tons (2), having replaced
traditional materials such as wood, stone, horn, ceramics, glass, leather, steel,
concrete, and others. They are multitalented, durable, cost effective, easy to
process, impervious to water, and have enabled applications that were not
possible before the materials’ availability.
Plastics, which consist of polymers and additives, are defined by their set of
properties such as hardness, density, thermal insulation, electrical isolation, and
primarily their resistance to heat, organic solvents, oxidation, and microorgan-
isms. There are hundreds of different plastics; even within one type, various
grades exist (eg, low viscosity polypropylene (PP) for injection molding, high
viscosity PP for extrusion, and mineral-filled grades).
Applications for polymeric materials are virtually endless; they are used as
construction and building material, for packaging, appliances, toys, and furniture,
in cars, as colloids in paints, and in medical applications, to name but a few.
Plastics can be shaped into films, fibers, tubes, plates, and objects such as bottles
or boxes. They are sometimes the best available technology. Many plastic products
are intended for a short-term use, and others have long-term applications (eg,
plastic pipes, which are designed for lifetimes in excess of 100 yr).
On the other hand, there is a growing debate about crude oil depletion and
price volatility, and environmental concerns with plastics are becoming more
serious. Approximately half of all synthetic polymers end up in short-lived
products, which are partly thermally recycled (burnt), but to some extent end
up on landfills or, worse, in the oceans, where large plastic objects are washed
ashore, sink or float (eg, the ‘‘North Pacific Garbage Patch,’’ which has continental
dimensions), and get fragmented to ‘‘microplastics’’ (particles between a few mm
and <5 mm) that harm and kill various organisms, finally ending up on our plates.
It is estimated that globally some 900 billion plastic bags (shopping bags, waste
bags, etc) are produced each year, with a typical average useful life of only a few
minutes and a significant fraction of them ending up as litter in the environment
(3), having wasted energy, spoiling the scene, and seriously harming wildlife.
1
Kirk-Othmer Encyclopedia of Chemical Technology. Copyright # 2015 John Wiley & Sons, Inc. All rights reserved.
DOI: 10.1002/0471238961.koe00006
2 BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE
Recycling plastics is not always feasible, and it can have a negative eco-
balance due to the efforts for collecting, sorting, and processing them. In most
cases, they need to be washed, and waste grinding and processing are energy
consuming. The recycling rate of plastics differs from country to country; there are
also differences in the plastics concerned. In the United States, the recycling rate
for polyethylene terephthalate (PET) packaging (bottles) was 31.2% in 2013 (5).
PET has the highest value of commodity plastics and is used mainly for drinking
bottles; hence, efforts are made to collect it. Recycled plastics go through different
processing steps such as sorting and melt filtration. They can often only be used in
lower grade products, typically not with direct food contact or high performance
applications. A ‘‘usage cascade’’ can be created, ending in thermal recycling
(combustion: incineration or pyrolysis).
To summarize, the extensive use of plastics has become a problem in many
aspects. Therefore, growing interest in ‘‘bioplastics’’ is observed (for reuse and
recycling of bioplastics, an unsolved issue, see Reference 6 and Section 9).
The term ‘‘bioplastics’’ stands for ‘‘biobased polymers.’’ According to IUPAC,
a bioplastic is derived from ‘‘biomass or . . . monomers derived from the biomass
and which, at some stage in its processing into finished products, can be shaped by
flow’’ (7).
In the area of bioplastics, several terms are used vaguely, ambiguously, or
wrongly. Hence, some important definitions are provided as follows (see also
Reference 7).
Plastics (plastic materials) in general are a huge range of organic solids
that are malleable (pliable, moldable). Malleability is a material’s ability to
deform under compressive stress. Plastics usually consist of organic polymers
with high molecular weight and other substances (fillers, colors, and additives).
They are typically synthetically produced. The term ‘‘natural plastics’’ is some-
times used in the industry for unfilled and uncolored plastics, as opposed to
compounds.
BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE 3
Often, the expression bioplastics is used to make a distinction from polymers
derived from fossil resources (monomers). The term is, to some extent, misleading,
4 BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE
as the prefix ‘‘bio’’ suggests that any polymer derived from biomass is environ-
ment-friendly.
Biobased polymers are neither necessarily biocompatible nor biodegradable.
According to industry association European Bioplastics, bioplastics are
‘‘polymers that are biobased, biodegradable, or both’’ (8). So the industry has
adopted a rather large definition. An alternative expression could be ‘‘technical
biopolymers.’’
In case polymers are obtained from agro-resources such as polysaccharides
(eg, starch) (9), one can talk about ‘‘agro-polymers.’’
‘‘Biomaterials’’ denote materials that are exploited in contact with living
tissues, organisms, or microorganisms. Hence, ‘‘polymeric biomaterials’’ are
used in applications such as medicine (catheters, bone cements, and contact
lenses) (10). Many of them are conventionally produced polymers. Implantable
biomaterials are PET, PP, PEEK (polyetheretherketone), UHMWPE (ultrahigh
molecular weight polyethylene), and PTFE (polytetrafluoroethylene) (11,12), on
the one hand, and (bio-)resorbable polymersPGA (polyglycolide), PLA (polylac-
tide), PCL (polycaprolactone), and PGS (poly(glycerol sebacate)), on the other
hand (12,13).
Generally, a polymer is a substance composed of macromolecules.
A macromolecule is a very large molecule commonly made by polymerization
of smaller subunits. In biochemistry, the term is applied to the main biopolymers
such as nucleic acids (eg, DNA), proteins, and carbohydrates (natural polymers),
plus other large, nonpolymeric molecules such as lipids and polyphenols. Natural
polymers (‘‘biopolymers’’) can be organic or inorganic (14), the latter having a
skeleton devoid of carbon (15). Examples for the former include cellulose, starch,
latex, and chitin; examples for the latter include polyphosphazenes, polysilicates,
polysiloxanes, polysilanes, polysilazanes, polygermanes, and polysulfides. In
between, one can find so-called hybrid polymers, ie, polymers containing inorganic
and organic components such as polydimethylsiloxane (silicone rubber: - -[O--Si
(CH3)2]n --).
Synthetic polymers (artificial polymers) are man-made polymers. They are
built from monomers by polymerization, polycondensation, or polyaddition. Most
synthetic polymers have significantly simpler and more random (stochastic)
structures than natural ones. They show a molecular mass distribution, which
does not exist in biopolymers (polydispersity vs monodispersity). They are sub-
stances that are not produced by nature (xenobiotics). Due to their high molecular
weight, they are not mobile. From a practical processing point of view, synthetic
polymers can be classified into the four main categories: thermoplastics (thermo-
softening plastics), thermosets (duromers), elastomers, and synthetic fibers. The
most common synthetic polymers are
• polyethylene (PE: PE-HD and PE-LD, with HD being high density and LD
being low density);
• polypropylene;
• acrylonitrile–butadiene–styrene (ABS);
• polyethylene terephthalate;
BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE 5
• polycarbonate (PC);
6 BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE
Fig. 1. Typical applications of polymers. The sizes of the bubbles show the relative
importance. PS-E ¼ expanded PS; ASA ¼ acrylonitrile–styrene–acrylate; SAN ¼ styrene–
acrylonitrile; other eng. ¼ other engineering plastics. (Source: Reference 2.)
After food and textiles, the ‘‘organic trend’’ is continuing to spread into materials;
bioplastics have come en vogue and receive extensive media attention, although
current production volumes are only on the order of 1% of annual plastics
manufacturing.
Increasing oil prices, rising consumer consciousness and environmental
awareness, improving feedstock and process economics, better product quality,
and scale of operation have helped ‘‘revive’’ bioplastics (see Section 5).
Other factors that motivate R&D in bioplastics are as follows:
11,000 microplastic particles per year (27). For images of microplastics ingested by
various animals, see, eg, the Swiss exhibition ‘‘Plastics Garbage Project’’ (28).
3.1. Environmental Aspects of Plastics. Major environmental
aspects of plastics include raw material consumption, energy use (29), and
pollution. Before the ban of CFCs (chlorofluorocarbons), the production of foamed
polystyrene (expanded polystyrene (EPS) and extruded polystyrene (XPS)) has
contributed to the destruction of the ozone layer. The production of plastics is a
rather energy-intensive process (29,30). Recycling of plastics is mostly impeded by
the lack of efficient sorting techniques. Apart from combustion, pyrolysis into
hydrocarbon fuels is feasible, but not yet carried out on an industrial level. As for
the effect of plastics on climate change (31), there is a mixed contribution;
petroplastics that are burnt (‘‘thermal recycling’’ into electricity and heat at
waste-to-energy plants) release CO2 into the atmosphere. In long-term applica-
tions and on landfills (which is increasingly banned, though), they become carbon
sinks. Over their useful life, lightweight plastics can help reduce transportation
emissions, eg, when used in cars instead of heavier materials, or when being
deployed as packaging material as opposed to glass or metal. For instance, it was
estimated that packaging beverages in PET bottles rather than glass bottles or
metal cans will save 52% of transportation energy (32). According to industry
association Plastics Europe, 5% less weight in a car translates on average into fuel
savings of 3%. Life cycle assessments are necessary to find the net contribution.
Plastics are generally perceived less environment-friendly than other mate-
rials such as paper, concrete, steel, and aluminum, partly due to lobbying
activities (33,34).
3.2. Plastics: Pros and Cons. Plastics and bioplastics in particular do
have several advantages. Table 5 provides a list of major pros and cons.
An environmental preference spectrum for plastics, exemplarily worked out
for the healthcare industry, is shown in Figure 3.
One can see from Figure 3 that bioplastics are assessed as most preferential
from an environmental point of view. The sustainability enhancement of bio-
plastics over conventional petrochemical-based plastics is depicted in Table 6.
Main sustainability drivers are energy savings and greenhouse gas emis-
sion cuts, apart from biodegradability and compostability. The environmental
and occupational health and safety hazards of biobased plastics are discussed in
Table 7.
The environmental impacts of biobased plastics are discussed in Table 8.
BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE 1
Table 9 presents a comparison of a bioplastic (polyhydroxybutyrate (PHB))
with a conventional commodity polymer (PP) in 10 categories (see also Table 8).
10 BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE
Table 7. Environmental and Occupational Health and Safety Hazards of Biobased Plastics
Bioplastic Environmental hazards Occupational health and safety
hazards
polyhydroxyalkanoates feedstock is grown using requ
methods of industrial irem
agricultural production, ents;
including GMOs; data on emis
energy requirements are sions
controversial of
4. Degradation of Plastics
Some modes of degradation require that the plastic be exposed at the surface
(UV light, O2), whereas other modes are only effective under special conditions of,
eg, industrial composting systems. There are also additives for polymers intended
to enhance their degradability (42,43).
For instance, BASF has been on the market for a decade with a compostable
bioplastic made from fossil sources (Ecoflex) and one made from renewable
sources (Ecovio). An overview of commercial compostable bioplastics is given,
eg, in the UL database (44).
Table 10 lists several biodegradable polymers from renewable and petro-
chemical resources.
For details on compostability of plastics, see Reference 45.
5. History of Bioplastics
Natural plastic materials (chewing gum, shellac) have been used for thousands of
years. In ancient times, natural plant gum was deployed to join pieces of wood in
house building, and natural plant gum was applied as a waterproof coating to
boats (46). Natural rubber came to the attention of Christopher Columbus in 1495,
when he had landed on the island of Haiti and saw people playing with an elastic
ball. Starch has been used for centuries as glue for paper and wood and as gum for
the textile industry (47).
BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE 19
20 BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE
The first plastics in the modern sense were produced in the end of 19th and
beginning of 20th century. Celluloid and cellophane were the first ones, and they
were biobased.
Natural rubber was originally derived from latex, a milky colloidal suspen-
sion found in special trees. Its first use was cloth waterproofed with unvulcanized
latex from Brazilian rubber trees.
In 1839, Charles Goodyear discovered vulcanization of natural rubber
materials with sulfur for improving elasticity and durability. He also invented
Ebonite (1852), a very hard rubber.
The first man-made plastic was Parkesine (1856), which was obtained from
cellulose treated with nitric acid. Bakelite, the first fully synthetic thermoset, was
invented in 1907. The material, polyoxybenzylmethylenglycolanhydride, is
obtained in an elimination reaction of phenol with formaldehyde. Another early
bioplastic, casein, was produced from milk proteins and lye. Casein, a family of
related phosphoproteins, is still used today for paints, glues, and in cheesemaking.
Galalith (invented around 1897) is a synthetic plastic material manufactured
from casein and formaldehyde. Galalith was used for buttons around 1930.
In 1941, Henry Ford presented the ‘‘soybean car,’’ a plastic-bodied car shown
at Dearborn Days, an annual community festival. It was 1000 lb lighter than a
steel car; probably, the composition was ‘‘soybean fiber in a phenolic resin with
formaldehyde used in the impregnation’’ (48).
Mass production of ‘‘conventional’’ petrochemical mass polymers such as PE,
PP, PVC, PET, and PVC started around 1940–1950. Cheap crude oil has made
possible the mass production of these petrochemical polymers, and bioplastics
virtually disappeared (compare the case of fuels, where biobased fuels that were
initially used for combustion were replaced by petrol and diesel).
Modern bioplastics started emerging in the 1980s, when people wanted to
reduce the volume of waste in landfills. They hoped that degradable plastics
discarded into landfills would take up less space once decomposed. This concept,
however, failed, because landfills are sealed and oxygen, water, and sunlight are
hardly available to break down the material.
Another concept that helped revive the interest in bioplastics was to reduce
the use of petrochemicals for plastics production, as the price of crude oil became
unstable and started to rise (see oil crises of the 1970s). The first biopolymers were
blends of starch with conventional polymers, so that a certain biodegradability
and use of natural feedstock were partly achieved.
Packaging, an area where plastic products have a short useful life, is
currently one of the biggest markets for biopolymers, such as biodegradable
plastic bags, compostable waste collection bags, and biodegradable or compostable
food packaging.
Cheap oil and performance issues have retarded progress in biopolymers,
despite growing customer concern about the environment.
In 2005, the chemical company Dow decided to pull out of bioplastics ‘‘due to
slow sector maturation’’ after having invested an estimated $750 million (49). In
2012, bioplastics company Metabolix reduced its production capacity of PHA from
50,000 to 10,000 ton/yr (1), as sales volumes were too low at that time. Other
BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE 21
manufacturers have been successful in mass producing bioplastics, eg, Brazil’s
Braskem (biobased PE made from sugarcane) or US NatureWorks (PLA).
22 BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE
Source: Ref. 53. PHB, poly[(R)-3-hydroxybutyrate]; PHAMCL, medium chain length PHA; PHBV, copolymer of (R)-3-hydroxybutyrate and (R)-3-
hydroxyvalerate.
18
BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE 19
Fig. 4. Metabolic engineering of high yielding biomass and oilseed crops for the copro-
duction of PHB and lignocellulosic biomass or seed oil. Large-scale production of PHB in
plants has the potential to provide a renewable cheap source of polymeric material that can
be used for the production of plastics, chemicals, and feed supplements with lignocellulosic
or seed oil coproducts that can be used to produce energy. Transmission electron micro-
graphs from thin sections of switchgrass leaf tissue and Camelina mature seeds are shown
in the insets and illustrate the accumulation of PHB in the form of granules in a bundle
sheath leaf chloroplast (switchgrass, top inset) and a seed plastid (Camelina, bottom inset),
respectively. (Reprinted with permission from Reference 53. # 2015, Elsevier.)
Fig. 5. Different families of biodegradable polymers and their raw materials. (Source:
Reference 41.)
20 BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE
medical applications. Since the project covers the entire value chain from growing
sugarcane to producing the biopolymer (1), it is competitive to conventional
polymer production.
7.2. Biobased PP. Polypropylene, the second most common commodity
plastic, can likewise be made from renewably sourced feedstock. Propylene is
accessible from methane via ethylene dimerization followed by metathesis (58).
Braskem has announced plans to build a 30,000–50,000 ton/yr biobased PP
production plant (1). A major market for biobased PP is the automotive industry,
as approximately 50% of plastic in cars is PP. For details, see, eg, Reference 59.
7.3. Biobased PET. The third most common thermoplastic is PET. It is a
thermoplastic polymer resin of the polyester family. It is mainly used for synthetic
fibers (then called ‘‘polyester’’) and for packaging, primarily bottles. The monomer
ethylene terephthalate (bis(2-hydroxyethyl) terephthalate) can be synthesized by
esterification between terephthalic acid and ethylene glycol, or by transesterifi-
cation between dimethyl terephthalate with ethylene glycol. Polymerization is
done through a polycondensation reaction of the monomers, carried out immedi-
ately after esterification/transesterification. Biobased PET can contain renewable
monoethylene glycol (MEG), produced, eg, from sugarcane-derived ethylene, as
being promoted by Coca Cola under the name Plantbottle (60,61). Its competitor
Pepsi has announced a 100% renewable PET material (62). Scale-up to commer-
cial production has been a hurdle so far (1) to replace conventional PET by a fully
biobased alternative. Plantbottle PET is produced from terephthalic acid (70% by
mass) and ethylene glycol (30% by mass), the latter coming from renewable
ethanol. The formulation is also termed Bio-PET 30. An alternative to PET is
the bioplastic polyethylene furanoate (PEF), which is expected to become com-
mercially available as of 2016 (63). The bacteria Nocardia can degrade PET with
its esterase enzyme (64).
7.4. Biobased PVC. PVC has been envisaged as one of the least environ-
ment-friendly synthetic polymers, setting free HCl and supporting dioxin forma-
tion in combustion. On top, soft PVC contains plasticizers with special
environmental challenges, eg, phthalates, so the material’s reputation is not so
high. Company Solvay from Belgium has announced the production of 60,000 ton/
yr of biobased ethylene for the production of PVC (1). Also, efforts are underway to
create biobased plasticizers for the replacement of phthalates. There are over 300
known plasticizers, with 50–100 being used commercially (65).
7.5. Biobased PC. Polycarbonates are situated between commodity
plastics and engineering plastics, as they exhibit an interesting combination of
temperature resistance, impact resistance, and optical properties. Conventional
polycarbonate is made from toxic monomers, bisphenol A (BPA), and phosgene
(COCl2).
An alternative polycarbonate can partly be made from isosorbide (derived
from glucose: hydrogenation of glucose gives sorbitol, and isosorbide is obtained by
double dehydration of sorbitol): Companies Mitsubishi and Roquette have
announced pilot plants for making isosorbide and incorporating it into PC (66).
Manufacturing PC from isosorbide and a diaryl carbonate removes the need to use
phosgene and bisphenol A in the process (1). The biobased PC is seen as still far
BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE 21
from commercialization (1). In Reference 67, the potential of a derivative of
cashew nutshell liquid (CNSL) as an alternative to BPA is discussed.
22 BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE
7.6. Biobased PU. Polyurethanes (PU, RPUR, and BUR) are thermo-
setting polymers commonly formed by reacting a di- or polyisocyanate with a
polyol. Applications are rigid foams. The polyols can be obtained from plant oil to
make a biobased PU. Natural oil polyols (NOPs, biopolyols) (68) are derived from
vegetable oils. Castor oil is suited best, as it consists mainly of ricinoleic acid,
which has hydroxyl groups. Other vegetable oils such as canola oil, peanut oil, or
soybean oil need to be treated to introduce--OH groups, mainly by double bond
oxidation.
7.7. Cellulose Acetate. Cellulose esters are another important group of
bioplastics. The most common cellulose esters comprise CA, cellulose acetate
propionate (CAP), and cellulose acetate butyrate (CAB). They are thermoplastic
materials produced through esterification of cellulose (45). Applications are
synthetic fibers, cigarette filters, and formerly photography film.
7.8. Polylactic Acid. Polylactic acid or polylactate is obtained from the
monomer lactic acid, which is produced from the microorganism-catalyzed
fermentation of sugar or starch. It is similar in properties to PET and has
FDA approval for food contact. Common raw materials are corn starch, sugar-
cane, and tapioca (starch extracted from cassava root). Chemically, PLA is not a
polyacid (polyelectrolyte), but rather a polyester. Companies active in the field
are, eg, NatureWorks, Purac, and Teijin (1). PLA is used for yogurt cups, where
it replaces polystyrene. Due to inferior material properties (heat resistance,
impact resistance, and low glass transition temperature), PLA is often blended
with conventional petroplastics. Costs of PLA have improved over the last
decade and are expected to go down further as capacity is added, eg, by
NatureWorks (140,000 ton/yr) and Purac (750,000 ton/yr) (1). NatureWorks’
Ingeo is manufactured in a two-step process that starts with fermenting the
dextrose derived from hydrolysis of corn starch. The product of the dextrose
fermentation, lactic acid, is further treated to create the intermediary monomer
lactide (the cyclic diester of lactic acid), which is then polymerized through
opening polymerization (39).
Polylactic acid and its copolymers can also be obtained from engineered
Escherichia coli (69).
Composite materials of PLA, eg, with woven bamboo fabric, have been
reported (70).
PLA is subject to abiotic degradation (ie, simple hydrolysis of the ester bonds
without requiring the presence of enzymes). It is also biocompatible.
Monomer stereochemistry (D- and L-lactic acid) can be controlled to impart
targeted utility in the final polymers (71), by the relative contents of both
homopolymers (D, L) and copolymers. Polymerization of a racemic mixture of L-
and D-lactides usually yields poly-DL-lactide (PDLLA), which is amorphous.
Recycling of PLA, eg, to repolymerizable oligomer (72), is challenging. PLA
has a strong potential for future use, spearheading bioplastics proliferation, since
it is comparatively cheap and available on the market.
PLA contamination in PET recycling is a topic of concern. The bio-
degradation of a PLA cup over 2 months is shown in Figure 6.
Thermoreversible cross-linked PLA (TCP) for rewritable shape memory is
BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE 21
described in Reference 48. For details on PLA, see References 46 and [74]74–76 for
applications.
22 BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE
Fig. 6. Biodegradation of a disposable cup made from PLA. Time sequence: 1, 15, and
30 days (top); 45 and 58 days (bottom). (Source: Reference 73.)
Fig. 8. Transmission electron microscope images: microbial cells containing native PHB
granules (a), cells with damaged walls in acid pretreatment (b), PHB granules with
attached residual cell mass (c), and purified PHB granules (d) (Source: Reference 84.)
Most commercial products are injection molding grades. PHAs are sold, eg,
by company Metabolix. Issues that limit commercialization of PHA are their
brittleness, a narrow processing window, a slow crystallization rate, and sensi-
tivity to thermal degradation (1). Similar to PLA, material shortcomings can
partly be overcome by blending with additives and other polymers. PHB is similar
in properties to PP (see Table 12).
For a comparison of PHB and PP, see also Reference 36.
The production rate of PHB-forming bacteria varies depending on substrates
and process conditions (see Table 13).
24 BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE
Table 13. PHB Production by Bacillus sp. with Different Carbon Sources
Carbon source Dry cell weight, g/L PHB, g/L % PHB, w/w
dextrose 12.58 5.02 39.90
xylose 13.408 5.02 37.44
sucrose 9.316 4.97 53.35
rhamnose 9.402 5.01 53.28
mannitol 9.942 5.00 50.29
maltose 8.636 4.88 56.51
lactose 8.502 5.06 59.52
mannose 9.114 4.97 54.53
galactose 15.494 4.92 31.75
starch 17.312 5.05 29.17
raffinose 8.37 5.07 60.57
Source: Ref. 86.
Agro and food wastes can also be used for PHA production, eg, rice husk,
wheat bran, mango peel, potato peel, bagasse, and straw (87).
PHAs degrade fastest in anaerobic sewage and slowest in seawater. The
degrading microbes colonize the polymer surface and secrete PHA depolymerases.
Reactions are as follows:
Reactive extrusion can be used for grafting functional groups onto the PHA
backbone by a solvent-free process.
For details on PHB, see References 88–96.
7.10. Polybutylene Succinate. Polybutylene succinate, sometimes
written as polytetramethylene succinate, is a thermoplastic, biodegradable ali-
phatic polyester with properties that are comparable to polypropylene. It is made
from succinic acid and 1,4-butanediol (BDO). Companies active in the field are, eg,
BioAmber, Reverdia, Myriant, and Purac (1).
7.11.BIOPLASTICS:
Polyvinyl Alcohol. Polyvinyl
BIOBASED alcohol
PLASTICS (PVOH, PVA) is 25
AS RENEWABLE a bio-
degradable water-soluble polymer (97).
26 BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE
Fig. 9. Extruded starch foam. (Reprinted with permission from Reference 102. # 2015,
Elsevier.)
biodegradable. Cellophane is used for food packaging and also to wrap cigars, as it
allows them to ‘‘breathe’’ (the material is permeable to moisture). Note that the
term ‘‘cellophane’’ has become genericized, so it is often used informally to refer
plastic film products of other materials, too.
7.17. Polyesteramides. Polyesteramides (PEAs) are bioabsorbable. They
can also be made from renewable resources. For details, see Reference 105.
7.18. Alginate. Alginate (alginic acid, algin) is a polysaccharide acquired
from the cell walls of brown algae. Alginate has been exploited for a long time as a
polyelectrolyte material (99). It can absorb 200–300 times its own weight in water.
Alginates can be used for films and coatings (106), particularly of edible products.
7.19. Polycaprolactone. PCL is a biodegradable polyester. It has a very
low melting point of around 600C. The most common use of polycaprolactone is in
the manufacture of speciality polyurethanes. Biomedical applications include
surgical suture.
Its physical properties make it a very tough, polyamide-like plastic that
melts to a consistency like putty at only 600C. This makes PCL attractive for the
hobbyist market and for rapid prototyping (softening can be achieved by immer-
sion in hot water).
7.20. Polytrimethylene Terephthalate. Polytrimethylene terephthal-
ate (PTT) is a new type of polyester. It has been applied to carpet and textile fibers,
monofilaments, films, nonwoven fabrics, and in the engineering thermoplastics
area (107). PTT is made from 1,3-propanediol (PDO), which can be obtained via
several renewable routes, eg, by aerobic fermentation from glycerol or glucose.
The bioprocess of PDO production was found to consume 40% less energy and to
cut greenhouse gas emissions by 20% compared with petroleum-based propane-
diol (107). PTT is sold by DuPont as Sorona.
7.21. Polyglycolic Acid. Polyglycolic acid or polyglycolide is a bio-
BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE 29
degradable, thermoplastic polymer. It constitutes the simplest linear, aliphatic
30 BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE
polyester. The glycolic acid is derived from glucose, eg, from sugar beets, and
glycolic acid is polymerized by polycondensation or ring-opening polymerization.
PGA is a tough fiber-forming polymer. PGA and its copolymers, eg, (poly(lactic-co-
glycolic acid) with lactic acid and poly(glycolide-co-caprolactone) with caprolac-
tone, are used for the manufacture of absorbable sutures.
7.22. Poly(butylene adipate-co-terephthalate). Poly(butylene adi- pate-
co-terephthalate) (PBAT) is a copolyester of adipic acid, 1,4-butanediol, and
dimethyl terephthalate. It is marketed as biodegradable alternative to PE, eg,
by BASF under the name Ecoflex and, blended with polylactic acid, as Ecovio.
7.23. Other Bioplastics. There are significantly more bioplastics under
investigation or even available on the market, such as a lignin-based thermoplast
(Arboform) (108) or gluten-based ones (9,109). They cannot be covered within the
scope of this article. For soy protein plastic (SPP) and sugar beet pulp (SBP)
plastics and composites, see Reference 110. For further bioplastics, see References
6, 111, and 112.
8. Biobased Additives
• Biobased lubricants.
• Glucose esters as biobased PVC plasticizers (113).
• Renewable air release additives (114).
• Renewable dimethyl succinate (DMS) as solvent and as a raw material for
pigments and UV stabilizers (115).
9. Recycling of Bioplastics
The generic options for bioplastics disposal are shown in Figure 10.
Recycling can be achieved by physical, biological, and chemical means.
Physical recycling can be considered an established technology.
BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE 31
The recycling industry has created a recycling code system from 1 to 7 for
plastics. The higher the number, the more difficult it is to deploy the material
profitably in useful post-consumer applications (see Fig. 11).
Figure 12 shows the four modes of biological treatment.
Chemical treatment can encompass hydrolysis/solvolysis, hydrothermal
depolymerization, and enzymatic depolymerization.
Thermal alternatives are incineration and pyrolysis. The former captures
the chemical energy, eg, for district heating from waste incineration plants, while
the latter aims at recycling the monomers. A variant is dry-heat depolymerization.
Waste treatment of bioplastics has been an active field of research; see
Figure 13 for the frequency of patent applications. Most of these patents are filed
in Japan and the United States.
Fig. 11. Resin identification codes (RICs) for physical recycling. Bioplastics all fall under 7.
32 BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE
Fig. 12. The four types of biological waste treatment for biopolymers: aerobic and anaero-
bic. Abbreviations: PBAT, poly(butylene adipate-co-terephthalate); PCL, poly(e-caprolac-
tone); PHA, polyhydroxyalkanoate; PLA, polylactide. (Source: Reference 6.)
Fig. 13. Patent applications on biopolymers and their waste treatment worldwide during
the period January 1, 1990 through August 31, 2012. (Source: Reference 6.)
others. Bioplastics are not readily distinguishable from regular plastics. Corpo-
rations are making efforts to appear eco-friendly and green. Bioplastics (ie,
biodegradable plastics and compostable plastics) have to be tested to validate
claims (119).
Ambiguous and competing terminology is used in marketing; see Figure 14
as an example.
In the United States, the Federal Trade Commission controls environmental
claims in the U.S. Code of Federal Regulations (CFR) Section 16, Part 260 (16 CFR
260)—Guides for the Use of Environmental Marketing Claims. Similar provisions
exist in other countries.
Clear labeling and certification can help distinguish between conventional
and biobased plastics. Labels to indicate a certain product quality are well
established on the consumer market, eg, for organic food, energy efficiency,
and fair trade.
Independent and internationally respected labels provide transparent and
accurate information for customers, and they help maintain a good reputation of
the bioplastics industry. Ideally, labels are linked to a recognized standard.
Currently, several (voluntary) certification systems exist worldwide with
regard to compostability, eg, DIN CERTCO, VincS otte and European Bioplastics
(Europe), BPI (USA), JBPA (Japan), and ABA (Australia). These systems are all
based on the same international standards (EN 13432, ASTM D6400, and ISO
BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE 31
17088) with similar requirements, but nevertheless show some minor and some-
Q2 times. In the United States, the percentage of biobased ingredients required for a
30 BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE
Fig. 15. Compostability logos used in different countries. (Source: References 122 and 123.)
Fig. 16. Markets for bioplastics (2012 data). (Source: Reference 8.)
Poultry feathers, which contain over 90% keratin, and of which >4 billion
pounds are generated in the U.S. poultry industry each year alone, have been
envisioned for bioplastics production (125), as fiber filler. As shown in Figure 16,
the main applications for bioplastics are seen in packaging, the automotive
industry, and agriculture.
11.1. Packaging. In the plastics industry today, there is no larger market
segment than packaging, which consumes approximately 100 millions tons of
materials per year. In Western Europe, 50% of all goods are packaged in plastics.
11.2. Mulching Film. The purpose of a mulching film, a polymer film, is
to cover seeded areas in order to protect the growing plants from weeds and low
temperatures, and to preserve humidity. Such films act as local greenhouses.
Traditional mulching films made from black PE had to be collected and discarded.
Biodegradable mulching films will decompose. They have environmental advan-
tages of photodegradable polyethylene films that are only fragmented and not
totally degradable.
11.3. Microbeads in Cosmetics. Plastic waste that ends up in the
oceans is fragmented into small particles called ‘‘microplastics.’’ Fish and birds
that take it for food eat these particles and inflict damage. Apart from containing
and releasing toxic products, microplastics were found to act as concentrators for
toxins (126) and persistent organic pollutants (POPs) (127). The microplastics
become enriched in the food chain and end up on humans’ plates (126). Also, small
polyester fibers from washing operations end in the environment. On top, several
cosmetics such as facial scrubs, toothpastes, and shower gels deliberately contain
microbeads of plastics. These microexfoliants serve the purpose of peeling. They
BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE 33
are too small to be filtered by sewage treatment plants. Biodegradable alterna-
tives are, eg, alginate, chitosan, and gelatin microbeads (128).
34 BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE
Brand owners seek solutions for a ‘‘green,’’ ‘‘eco-friendly’’ image, speaking about
corporate social responsibility (CSR), and consumers are looking for sustainable—
yet cost-effective—products. The development and widespread acceptance and
proliferation of bioplastics have to face several challenges. Today, bioplastics can
be considered to be in their infancy, yet there is significant potential. In the near
term, blending with polyolefins and other petrobased plastics is a viable approach
to start using them, contributing to sustainability, while concurrently working to
improve performance and costs (17).
Bioplastics are commonly, without questioning, promoted as a ‘‘green’’
alternative to regular plastics; however, matters are more complex. A case-by-
case life cycle assessment has to show whether their impact on the environment is
really superior to that of conventional plastics. The following aspects have to be
considered:
Fig. 17. Cost split for a mid-sized PLA plant. (Source: Reference 131.)
Also for bioplastics, economies of scale apply, so pilot plants cannot compete with
established, large petroplastics plants, and new commercial bioplastics plants are
typically smaller than petrochemical ones.
Fig. 18. Market size for bioplastics. (a) Biobased vs biodegradable materials. (b) Split by
material. (Source: Reference 8.)
Figure 18, showing data for 2012, estimates the global market size for bioplastics
to amount to 1.4 million ton/yr, which is roughly 0.5% of the total current market
for (new) plastics.
One-third of global bioplastics is manufactured in South America (2) (see Fig.
19). Figure 19 also shows a projection for bioplastics market size in 2017. One can
see that the nonbiodegradable bioplastics will strongly increase, whereas bio-
degradable plastics will see only moderate growth (see also Section 14).
BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE 39
Fig. 19. Global bioplastics production (2012 data) by region (a) and type (b). (Source:
European Bioplastics/University of Applied Sciences and Arts, Hanover (8).)
40 BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE
The growth in bioplastics is driven by the expansion in demand. One can observe
a shift from compostable (biodegradable) to durable bioplastics, away from
single-use applications such as disposable bags or plastic cutlery toward
more valuable, high performance goods such as automotive parts and household
appliances. This trend is coupled with an increase in biopolymer products’
performance (132).
The production capacity of 3.5 million tons in 2011—one-third of which
was utilized—is expected to triple to nearly 12 million tons by 2020 (132).
With an estimated total polymer production of roughly 400 million tons in
2020, the biobased share would then have increased from 1.5% in 2011 to 3%
in 2020. The highest growth is expected in drop-in biopolymers. Biobased
PET should reach a production capacity of about 5 million tons by the year
2020, using bioethanol from sugarcane, followed by biobased polyolefins such
as PE and PP from the same feedstock. PLA and PHA are expected to at
least quadruple the capacity between 2011 and 2020. Most investment in
new biobased polymer capacities is estimated to happen in Asia and South
America because of better access to feedstock. Europe’s share in bioplastics
will decrease from 20 to 14% and North America’s share from 15 to 13%,
whereas in Asia it will increase from 52 to 55% and in South America’s from
13 to 18%. This means that each region of the world will see an increase in
bioplastics use (132).
15. Conclusions
The proliferation and use of bioplastics should not be determined by their relative
costs, but by their performance instead. Specific advantages for target applica-
tions need to be worked out. Bioplastics are not generally more environmentally
sound than conventional plastics. They can be based on renewable feedstock,
biodegradable, or both. Bioplastics currently only constitute approximately 1% of
global plastics production; however, a huge potential is seen. Drop-in bioplastics
have identical properties to their petrochemical counterparts, which has acceler-
ated their commercialization. ‘‘Green’’ PE and PET are already on the market, as
are PLA and starch blends. With consumer consciousness and sustainability
becoming new market drivers, the push to bring more bioplastics to commerciali-
zation has become stronger, improving properties and performance, and reducing
production cost (1).
By finding suitable monomers from renewable feedstock, a cost-effective
swap toward bioplastics is feasible, because no entirely new polymerization plant
has to be built, but only the upstream infrastructure is amended, eg, by a
fermentation unit or a catalytic cracker. The concept of a biorefinery (133) also
fits well into bioplastics, several high value products can be obtained from a given
feedstock/raw material mix, and integration brings costs down.
BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE 41
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MAXIMILIAN LACKNER
Vienna University of Technology, Vienna, Austria
BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE 41
Keywords/Abstract
Dear Author,
Keywords and abstracts will not be included in the print version of your article but only
in the online version. The abstract and keywords are included in the print version only
for your review.
Abstract:
Bioplastics are biobased polymers with two sustainability concepts: biodegradability and
renewability. On the one hand, bioplastics that biodegrade to CO2 and H2O in the
environment can be produced, eg, avoiding litter and damage to marine organisms. On the
other hand, renewable feedstocks instead of petroleum can be used, for instance, corn,
sugarcane, and algae, reducing dependence on crude oil and reducing the impact on the
climate. Currently, bioplastics have a market share ofrv1%, yet they experience annual
growth rates in excess of 20–30%. This article highlights some key aspects associated with
bioplastics, the performance of which can be tailored to meet that of petrochemical
polymers or to offer new properties, eg, by blending and additivation. Important
bioplastics are TPS (thermoplastic starch), PLA (polylactic acid), PHAs (polyhydroxyalk-
anoates), and bio-PE, bio-PP, and bio-PET, which contain at least some renewable carbon.
1. Please include the references cited in Table 8 in the reference list or else delete
them from the table body.
2. The intended meaning of the text ‘‘but nevertheless show some minor and
sometimes’’ is not clear. Please check.
3. Please provide the name(s) of the assignee(s) in Reference 43.