BIOPLASTICS: BIOBASED PLASTICS AS … · BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE AND/OR BIODEGRADABLE ALTERNATIVES TO PETROPLASTICS 1. Introduction ‘‘Plastics’’ were introduced

BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLEAND/OR BIODEGRADABLE ALTERNATIVES TOPETROPLASTICS

1. Introduction

‘‘Plastics’’ were introduced approximately 100 years ago, and today are one of themost used and most versatile materials. Yet society is fundamentally ambivalenttoward plastics, due to their environmental implications, so interest in bioplasticshas sparked.

According to the petrochemical market information provider ICIS, ‘‘Theemergence of bio-feedstocks and bio-based commodity polymers production, intandem with increasing oil prices, rising consumer consciousness and improvingeconomics, has ushered in a new and exciting era of bioplastics commercialization.However, factors such as economic viability, product quality and scale of operationwill 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 arederived from petrochemicals, exceeds 300 million tons (2), having replacedtraditional materials such as wood, stone, horn, ceramics, glass, leather, steel,concrete, and others. They are multitalented, durable, cost effective, easy toprocess, impervious to water, and have enabled applications that were notpossible before the materials’ availability.

Plastics, which consist of polymers and additives, are defined by their set ofproperties such as hardness, density, thermal insulation, electrical isolation, andprimarily their resistance to heat, organic solvents, oxidation, and microorgan-isms. There are hundreds of different plastics; even within one type, variousgrades exist (eg, low viscosity polypropylene (PP) for injection molding, highviscosity PP for extrusion, and mineral-filled grades).

Applications for polymeric materials are virtually endless; they are used asconstruction and buildingmaterial, 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 bottlesor boxes. They are sometimes the best available technology.Many plastic productsare 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 andprice volatility, and environmental concerns with plastics are becoming moreserious. Approximately half of all synthetic polymers end up in short-livedproducts, which are partly thermally recycled (burnt), but to some extent endup on landfills or, worse, in the oceans, where large plastic objects are washedashore, sink or float (eg, the ‘‘North Pacific Garbage Patch,’’ which has continentaldimensions), and get fragmented to ‘‘microplastics’’ (particles between a few mmand<5mm) that harm and kill various organisms, finally ending up on our plates.It is estimated that globally some 900 billion plastic bags (shopping bags, wastebags, etc) are produced each year, with a typical average useful life of only a fewminutes and a significant fraction of them ending up as litter in the environment(3), having wasted energy, spoiling the scene, and seriously harming wildlife.

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Kirk-Othmer Encyclopedia of Chemical Technology. Copyright # 2015 John Wiley & Sons, Inc. All rights reserved.

DOI: 10.1002/0471238961.koe00006

http://dx.doi.org/10.1002/0471238961.koe00006

It is estimated that since the 1950s, approximately 1 billion tons of plasticshave been discarded and some of that material might persist for centuries or evensignificantly longer, as it is demonstrated by the persistence of natural materialssuch as amber (4).

One of the biggest advantages of plastics, their durability, is likewise one oftheir biggest problems: The rate of degradation (biodegradation) does not matchtheir intended service life, and buildup in the environment occurs.

Recycling of waste plastics, in principle, a meaningful approach, can followdifferent routes:

1. Reuse of the product (eg, a bag).

2. Material recycling (collection, sorting, and reprocessing).

3. Feedstock recycling (depolymerization to capture the monomers).

4. Thermal recycling (use of the energy content in waste incineration, steelworks, or cement kilns).

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 mostcases, they need to be washed, and waste grinding and processing are energyconsuming. The recycling rate of plastics differs from country to country; there arealso differences in the plastics concerned. In the United States, the recycling ratefor polyethylene terephthalate (PET) packaging (bottles) was 31.2% in 2013 (5).PET has the highest value of commodity plastics and is used mainly for drinkingbottles; hence, efforts are made to collect it. Recycled plastics go through differentprocessing steps such as sorting andmelt filtration. They can often only be used inlower grade products, typically not with direct food contact or high performanceapplications. 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 manyaspects. Therefore, growing interest in ‘‘bioplastics’’ is observed (for reuse andrecycling 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 biomassand which, at some stage in its processing into finished products, can be shaped byflow’’ (7).

In the area of bioplastics, several terms are used vaguely, ambiguously, orwrongly. Hence, some important definitions are provided as follows (see alsoReference 7).

Plastics (plastic materials) in general are a huge range of organic solidsthat are malleable (pliable, moldable). Malleability is a material’s ability todeform under compressive stress. Plastics usually consist of organic polymerswith 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 tocompounds.

Often, the expression bioplastics is used to make a distinction from polymersderived from fossil resources (monomers). The term is, to some extent, misleading,

2 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 hasadopted a rather large definition. An alternative expression could be ‘‘technicalbiopolymers.’’

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 livingtissues, organisms, or microorganisms. Hence, ‘‘polymeric biomaterials’’ areused in applications such as medicine (catheters, bone cements, and contactlenses) (10). Many of them are conventionally produced polymers. Implantablebiomaterials are PET, PP, PEEK (polyetheretherketone), UHMWPE (ultrahighmolecular weight polyethylene), and PTFE (polytetrafluoroethylene) (11,12), onthe one hand, and (bio-)resorbable polymersPGA (polyglycolide), PLA (polylac-tide), PCL (polycaprolactone), and PGS (poly(glycerol sebacate)), on the otherhand (12,13).

Generally, a polymer is a substance composed of macromolecules.Amacromolecule is a very large molecule commonly made by polymerization

of smaller subunits. In biochemistry, the term is applied to the main biopolymerssuch as nucleic acids (eg, DNA), proteins, and carbohydrates (natural polymers),plus other large, nonpolymeric molecules such as lipids and polyphenols.Naturalpolymers (‘‘biopolymers’’) can be organic or inorganic (14), the latter having askeleton 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. Inbetween, one can find so-called hybrid polymers, ie, polymers containing inorganicand organic components such as polydimethylsiloxane (silicone rubber: ��[O��Si(CH3)2]n��).

Synthetic polymers (artificial polymers) are man-made polymers. They arebuilt from monomers by polymerization, polycondensation, or polyaddition. Mostsynthetic polymers have significantly simpler and more random (stochastic)structures than natural ones. They show a molecular mass distribution, whichdoes not exist in biopolymers (polydispersity vs monodispersity). They are sub-stances that are not produced by nature (xenobiotics). Due to their high molecularweight, they are not mobile. From a practical processing point of view, syntheticpolymers can be classified into the four main categories: thermoplastics (thermo-softening plastics), thermosets (duromers), elastomers, and synthetic fibers. Themost common synthetic polymers are

� polyethylene (PE: PE-HD and PE-LD, with HD being high density and LDbeing low density);

� polypropylene;

� acrylonitrile–butadiene–styrene (ABS);

� polyethylene terephthalate;

� polycarbonate (PC);

BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE 3

� polyvinyl chloride (PVC);

� polystyrene (PS);

� polyamides (PAs, eg, Nylon 6 and Nylon 66);

� Teflon (polytetrafluoroethylene);

� polyurethane (PU, PUR);

� poly(methyl methacrylate) (PMMA, acrylic).

They are nonbiodegradable. Note: Technically, all conventional plastics aredegradable. However, due to their slow breakdown, they are considered practi-cally non(bio)degradable.

Typical applications of polymers are shown in Figure 1.Semi-synthetic polymers are chemically treated polymers of natural origin.

An example is rubber. It is made from latex, the ‘‘milk’’ of Hevea brasiliensis(rubberwood), by vulcanizing it (cross-linking the polymer chains to a certainextent) using sulfur or S2Cl2. Another example is cellulose. Cellulose can bemodified in two different ways:

� It can be dissolved and precipitated again in a different physical shape, eg, toproduce viscose silk (rayon), using CS2.

� It can be chemically modified, using the three remaining OH groups of theglucose monomers, eg, to cellulose acetate (CA) with acetic acid, cellulosemethyl ethers with methanol, and cellulose nitrate with nitric acid.

Fig. 1. Typical applications of polymers. The sizes of the bubbles show the relativeimportance. PS-E¼ expanded PS; ASA¼ acrylonitrile–styrene–acrylate; SAN¼ styrene–acrylonitrile; other eng.¼ other engineering plastics. (Source: Reference 2.)


Thus, a ‘‘synthetic biopolymer’’ refers to a man-made biopolymer that isprepared using abiotic chemical routes. Table 1 shows the bonds in polymers.

Two common processing technologies for the economically important ther-moplastics are extrusion (continuous process, yielding, eg, window profiles orpipes) and injection molding (batch process, yielding, eg, dishes and cups).

Polymers (‘‘plastics’’) can be blended (17) and further processed to com-pounds and composite materials with different properties. Examples includeflame-retardant or colored polypropylene, talc-filled polypropylene (eg, forreduced thermal expansion in bumpers), NFRPs (natural fiber-reinforced plas-tics), and WPCs (wood plastic composites or wood polymer composites, ie, woodfibers in a polymer such as PE or PVC). NFRPs are used in automobiles,construction and furniture, and industrial and consumer products. Applicationsof WPCs are deckings, railings, window and door frames, and furniture; the mainmarket is currently in the United States. For composites and nanocompositesbased on cellulose, see, eg, Reference 18.

2. Motivation for and Types of Bioplastics

After food and textiles, the ‘‘organic trend’’ is continuing to spread into materials;bioplastics have come en vogue and receive extensive media attention, althoughcurrent production volumes are only on the order of 1% of annual plasticsmanufacturing.

Increasing oil prices, rising consumer consciousness and environmentalawareness, 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:

� Rural development: added value and jobs (bioplastics feedstock is typicallygrown in rural areas, where farmers can benefit).

� Interesting new properties or mix of properties (degradability, haptics,weight, etc).

� Feedstock diversification (less dependence on crude oil, which is finite).

Growth rates of bioplastics in excess of 20–30% have been witnessed forseveral years and several materials. These are expected to continue. There is a

Table 1. Typical Bonds in Polymers

Type of bond Natural examples Synthetic examples

carbon–carbon (��C��C��) polyolefins (eg, rubber) polyolefins (eg, polyethylene,polypropylene)

ester (��O��C��O��) nucleic acids (eg, DNA, RNA) polyesters (eg, Diolen, apolyester fiber)

amide (��C��O��NH��) polypeptides (eg, wool, silk,enzymes)

polyamides (eg, Nylon, apolyamide)

ether (��O��) polysaccharides (eg, starch,cellulose)

special plastics (eg, DuPont’sDelrin, a POM)

Modified from Ref. 16. POM¼polyoxymethylene.


substitution potential of up to 90% of the total consumption of plastics by biobasedpolymers (19). This concerns standard polymers such as PE, PP, PVC, and PET, aswell as high performance polymers such as PAs (see Table 2).

Bioplastics have two aspects: ‘‘green’’ educt and/or ‘‘green’’ product (where‘‘green’’ stands for ‘‘sustainable’’):

� Use of a ‘‘green’’ feedstock for the production of conventional polymers (so-called drop-in polymers): renewability.

� Synthesis of ‘‘green’’ polymers: biodegradability.

This is illustrated in Figure 2. As Figure 2 shows, a material that is eitherrenewable or biodegradable qualifies as biopolymer. There are also ‘‘partly bio-based’’ biodegradable and nonbiodegradable biopolymers, if, for instance, only oneblending partner or only part of the feedstock is derived from renewable resources(see Table 3).

The content of biobased carbon can be determined by radiocarbon analysisaccording to ISO 16620 and ASTMD6866-05 (22,23). Themeasurement has a highaccuracy. In this context, one can also talk about ‘‘hybrid’’ plastics (not to beconfused with those plastics that contain inorganic and organic components).

As can be seen fromFigure 2 and Table 3, bioplastics can be renewable and/ordegradable. They can contribute to sustainability (24) at ‘‘the cradle,’’ at ‘‘thegrave,’’ or both. The box in the bottom left of Figure 2 is ‘‘conventional plastics,’’whereas the other three boxes can be considered biobased polymers. The distinc-tion, due to the two dimensions, is somewhat blurred, since many plastics on themarket contain bioplastics to a certain extent in blends with conventionalpolymers.

Degradable bioplastics are intended for short-lived, disposable products.Biobased durable plastics are to replace conventionally produced plastic goods.

A bioplastic material can also fulfill both criteria. Polylactic acid, thermo-plastic starches (TPS), and polyhydroxyalkanoates (PHAs) are based on natural/renewable feedstock and exhibit biodegradation under various conditions. Prod-ucts such as biobased polyamides and biopolyethylene are fabricated from bio-derived feedstocks but are not degradable. On the other hand, polybutyleneterephthalate (PBT) and polybutylene succinate (PBS) are typically manufac-tured from petrochemical feedstocks but are biodegradable.

Table 2. Bioplastics Intermaterial Substitution Opportunities

Polyolefins Other polymers

LDPE LLDPE HDPE PP PS PVC PUR PET

starch polymers þþ þþ þþ þþ þ � þþ �PLA þ þ þþ þþ þþ � � þþPHA þþ þþ þþþ þþþ þþ þ þþ þþother polyesters � � � � � � � þþþbiobased-PE þþþ þþ þþþ � � � � �Source: Chemical Market Resources, Inc. (20). LDPE, HDPE: low-, high-density PE; PUR: poly-urethane; PLA: polylactic acid; PHA: polyhydroxyalkanoates; substitution potential: (þþþ) high,(þþ) medium, (þ) low, and (�) not foreseen.


Fig. 2. Types of bioplastics, both biodegradable and nonbiodegradable, and examples.(Reprinted with permission from Reference 21. # 2013, Elsevier.)

Table 3. Biodegradable vs Biobased Polymers

Biodegradable Nonbiodegradable

biobased CA, CAB, CAP, CN, PHB, PHBV,PLA, starch, chitosan

PE (LDPE), PA 11, PA 12, PET,PTT

partially biobased PBS, PBAT, PLA blends, starchblends

PBT, PET, PTT, PVC, SBR, ABS,PU, epoxy resin

fossil fuel-based PBS, PBSA, PBSL, PBST, PCL,PGA, PTMAT, PVOH

PE (LDPE, HDPE), PP, PS, PVC,ABS, PBT, PET, PS, PA 6, PA6.6, PU, epoxy resin, syntheticrubber

Source: Ref. 6. Abbreviations: ABS, acrylonitrile–butadiene–styrene; CA, cellulose acetate; CAB,cellulose acetate butyrate; CAP, cellulose acetate propionate; CN, cellulose nitrate; HDPE, highdensity polyethylene; LDPE, low density polyethylene; PA 6, polyamide 6; PA 6.6, polyamide 6.6; PA11, aminoundecanoic acid-derived polyamide; PA 12, laurolactam-derived polyamide; PBAT, poly(butylene adipate-co-terephthalate); PBS, polybutylene succinate; PBSA, poly(butylene succinate-co-adipate); PBSL, poly(butylene succinate-co-lactide); PBST, poly(butylene succinate-co-terephthal-ate); PBT, polybutylene terephthalate; PCL, poly(e-caprolactone); PE, polyethylene; PET, poly-ethylene terephthalate; PGA, polyglycolide; PHB, polyhydroxybutyrate; PHBV, poly(3-hydroxybutyrate-co-3-hydroxyvalerate); PLA, polylactide; PP, polypropylene; PS, polystyrene;PTMAT, poly(methylene adipate-co-terephthalate); PTT, polytrimethylene terephthalate; PVOH,polyvinyl alcohol; PVC, polyvinyl chloride; PU, polyurethane; SBR, styrene–butadiene rubber.


Bioplastics can reduce carbon dioxide emissions by 30–70% compared withconventional plastics (19).

‘‘Green chemistry’’ (or sustainable chemistry) can be understood as thedesign of chemical products and processes that reduce or eliminate the use orgeneration of substances that are hazardous to humans, animals, plants, and theenvironment, where energy efficiency should be high and the waste target is zero;as a consequence, costs should also be low. A ‘‘green polymer’’ is one that conformsto the concept of green chemistry. Note, however, that a green polymer does notnecessarily mean ‘‘environment-friendly polymer’’ or ‘‘biobased polymer.’’

So the motivation for bioplastics is sustainability. The principle for sustain-ability is simply explained: Whatever man needs for survival and well-beingdirectly and indirectly comes from our natural environment. Sustainable action isone that maintains conditions under which humans and nature coexist harmoni-ously andwhere social, economic, and environmental requirements of present andfuture generations are met.

3. Sustainability of Plastics and Bioplastics

A discussion of sustainability of plastics has to consider two main aspects: lifecycle assessment (LCA) and ecotoxicity. LCA, also referred to as eco-balance andcradle-to-grave analysis, is the investigation and valuation of the environmentalimpacts of a given product or service over its entire existence (input, life, andoutput), considering raw material sourcing, production process, packaging, dis-tribution, usage, andwastemanagement including transport (25). For details, see,eg, the standards ISO 14040 and ISO 14044.

Ecotoxicity subsumes the consequence of adverse effects caused by a sub-stance on the environment and on living organisms. The environment encom-passes water, air, and soil. When only living organisms such as animals, plants,and microorganisms are affected, the term ‘‘toxicity’’ should be used.

Pure plastics generally show low toxicity due to their insolubility in waterand since they are biochemically inert (because of a large molecular weight).Plastic products, in contrast, contain a variety of additives, some of which can betoxic (eg, phthalates as plasticizers). Also, residues of toxic monomers can stillexist in the product (eg, vinyl chloride, the precursor of PVC, a human carcinogen),or it can release such monomers or oligomers upon excessive heating (eg, PTFE).

Toxic substances can further be produced during incineration, particularlywhen it is carried out in an uncontrolled way (at low temperatures, dioxins, PAHs(polycyclic aromatic hydrocarbons), and other noxious fumes can be formed).

An increasing presence of microplastics was found in the marine food chain.Microplastics (debris <5mm) can occur in the environment as primary or second-ary microplastics (26). Primary microplastics are those manufactured for aspecific purpose, eg, for cosmetic products. Secondary microplastics are thoseproduced through environmental fragmentation of larger-sized products. Theirtypical abundance was reviewed in Reference 26 (see Table 4).

In a recent study of microplastics in bivalves cultured for human consump-tion, it was found that the two species investigated contained on average 0.36 and0.47 particles/g, which exposes the European shell fish consumer to an estimated


11,000microplastic particles per year (27). For images ofmicroplastics ingested byvarious animals, see, eg, the Swiss exhibition ‘‘Plastics Garbage Project’’ (28).

3.1. Environmental Aspects of Plastics. Major environmentalaspects of plastics include raw material consumption, energy use (29), andpollution. Before the ban of CFCs (chlorofluorocarbons), the production of foamedpolystyrene (expanded polystyrene (EPS) and extruded polystyrene (XPS)) hascontributed to the destruction of the ozone layer. The production of plastics is arather energy-intensive process (29,30). Recycling of plastics is mostly impeded bythe lack of efficient sorting techniques. Apart from combustion, pyrolysis intohydrocarbon fuels is feasible, but not yet carried out on an industrial level. As forthe effect of plastics on climate change (31), there is a mixed contribution;petroplastics that are burnt (‘‘thermal recycling’’ into electricity and heat atwaste-to-energy plants) release CO2 into the atmosphere. In long-term applica-tions and on landfills (which is increasingly banned, though), they become carbonsinks. Over their useful life, lightweight plastics can help reduce transportationemissions, eg, when used in cars instead of heavier materials, or when beingdeployed as packaging material as opposed to glass or metal. For instance, it wasestimated that packaging beverages in PET bottles rather than glass bottles ormetal cans will save 52% of transportation energy (32). According to industryassociation Plastics Europe, 5% less weight in a car translates on average into fuelsavings 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 lobbyingactivities (33,34).

3.2. Plastics: Pros and Cons. Plastics and bioplastics in particular dohave several advantages. Table 5 provides a list of major pros and cons.

An environmental preference spectrum for plastics, exemplarily worked outfor the healthcare industry, is shown in Figure 3.

One can see from Figure 3 that bioplastics are assessed as most preferentialfrom 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 environmentaland occupational health and safety hazards of biobased plastics are discussed inTable 7.

The environmental impacts of biobased plastics are discussed in Table 8.Table 9 presents a comparison of a bioplastic (polyhydroxybutyrate (PHB))

with a conventional commodity polymer (PP) in 10 categories (see also Table 8).

Table 4. Spatial Distribution and Abundance of Microplastics from Selected References

Location Maximum concentration observed, particles/km2

Italy, Lake Garda 1,108,000,000Portugal, beach 218,000,000northwestern Mediterranean Sea 1,000,000USA, Laurentian Great Lakes 466,000waters around Australia 839

Modified with permission from Ref. 26. # 2015, Elsevier.


‘‘CML 2 Baseline 2000 V2.03’’ mentioned in Table 9 is a database thatcontains characterization factors for life cycle impact assessment (LCIA). It isavailable at the University of Leiden (37).

It is found in this study that, in all of the life cycle categories, PHB issuperior to PP. Energy requirements are slightly lower than those for polyolefinproduction. PE impacts are lower than PHB values in acidification and eutro-phication (36).

Table 5. Pros and Cons of Petrobased and Biobased Plastics

Pros Cons

conventionalplastics

� low cost� good and excellent technicalproperties

� easy processability� can save energy and resourcescompared with other materials,depending on application

� thermal recycling possible(cascade use)

� based on petrochemicals� difficult to recycle� mostly not biodegradable� uncontrolled combustion canrelease toxic substances

� ecotoxicity, particularlymicroplastics in the marineenvironment

� partly toxic raw materials andadditives

bioplastics(compared withconventionalplastics)

� (partly) biodegradable� (partly) based on naturalfeedstock, hence reducing theemission of GHG and thedependence on crude oil

� interesting properties� generally, standardmanufacturing processes andplants can be used for biobasedfeedstock, and standardprocessing machines can be usedfor biobased plastics

� positive image among consumers

� costly� (partly) use of geneticallymodified organisms

� use of land, fertilizers, andpesticides for crops, potentialfood competition

� narrow processing window(lower melting temperature)

� brittleness� thermal degradation

Fig. 3. Environmental preference spectrum for the healthcare industry. (Reprinted withpermission from Reference 35. # 2012, Elsevier.)


Table 6. Sustainability Improvements of Biobased Plastics Relative to Petroleum-BasedPlastics (PBP)

Bioplastic Sustainability improvement

polyhydroxyalkanoates highly biodegradablepolylactic acid production uses 30–50% less fossil energy and

generates 50–70% less CO2 emissions than PBP;competitive use of water with the best performingPBP, recyclable, compostable at temperatures above60�C

thermoplastic starch production requires 68% less energy than its PBPcounterpart; lower CO2 emissions than PBP;biodegradable and compostable

biourethanes production requires 23% less energy and 36% lessGGH, compared with PBP

cellulose and lignin the biological degradation of lignin is lower thancellulose, compostable

polytrimethylene terephthalate production requires 26–50% less energy and 44% lowerGHG than its PBP counterpart; no chemicalsadditives are used; biodegradable; potentiallyrecyclable

Corn zein and soy protein biodegradable and compostable

Source: Ref. 35. GMOs: genetically modified organisms; GHG: greenhouse gases.

Table 7. Environmental and Occupational Health and Safety Hazards of Biobased Plastics

Bioplastic Environmental hazards Occupational health and safetyhazards

polyhydroxyalkanoates feedstock is grown usingmethods of industrialagricultural production,including GMOs; data onenergy requirements arecontroversial

exposure to pesticides; physicalextraction of PHAs usespyridine, methanol, hexane,or diethyl ether; chemicaldigestion uses sodiumhypochlorite, methanol, anddiethyl ether

polylactic acid feedstock is grown usingmethods of industrialagricultural production,including GMOs; 1-octanol isecotoxic and organic tin canbuild up in living organisms

exposure to pesticides, sulfuricacid, tin octoate, 1-octanol,and urea; finely pulverizedstarch can cause powerfulexplosions

thermoplastic starch feedstock is grown usingmethods of industrialagricultural production,including GMOs

exposure to pesticides, glycerol,and urea; finely pulverizedstarch can cause powerfulexplosions

biourethanes (BURs) feedstock is grown usingmethods of industrialagricultural production,including GMOs

exposure to pesticides, toluenediisocyanate (TDI),methylene diphenylisocyanate (MDI), tinderivatives

cellulose and lignin the process has relatively highenergy and waterrequirements; emissions of

exposure to elevatedtemperature and pressure;exposure to disulfide, sodium

(continued)


4. Degradation of Plastics

Biodegradable plastics had a difficult start, as marketing claims exceeded per-formance. ‘‘The U.S. biodegradables industry fumbled at the beginning by intro-ducing starch filled (6–15%) polyolefins as true biodegradable materials. These atbest were only biodisintegradable and not completely biodegradable. Data showedthat only the surface starch biodegraded, leaving behind a recalcitrant poly-ethylene material.’’ (38). This situation questioned the entire biodegradableplastics industry, and has kept consumers and regulators confused for the under-standing of biodegradability and compostability. There are currently 23 activestandards for testing the biodegradability or biobased content of plastics accordingto ASTM protocols (39). One has to discern between degradability in general andbiodegradability in specific. Biodegradability is the capability of being degradedby biological activity (note that the in vitro activity of enzymes cannot beconsidered as biological activity). Degradation is the lowering of the molar massesof macromolecules that form the substances by chain scissions. All biodegradablepolymers are degradable polymers, but not necessarily vice versa (note that

Table 7. (Continued)

Bioplastic Environmental hazards Occupational health and safetyhazards

pollutants to air and waterduring kraft process need tobe addressed

hydroxide, volatile toxic,flammable, and malodorousemissions of sulfur; exposureto propionic, acetic, sulfuric,and nitric acids

polytrimethyleneterephthalate

feedstock is grown usingmethods of industrialagricultural production,including GMOs; only 37%(by weight) from renewablysourced material GMOs areused in fermentation ofglucose to bio-PDO

exposure to pesticides,terephthalic acid, dimethylterephthalate, and methanol;finely pulverized starch cancause powerful explosions

corn zein and soyprotein

feedstock is grown usingmethods of industrialagricultural production,including GMOs

exposure to pesticides, alcoholor volatile solvents, alkalineand acid substances, andformaldehyde orglutaraldehyde

nanobiocomposites(cellulose and lignin)

the process has relatively highenergy and waterrequirements; emissions ofpollutants to air and waterduring kraft process need tobe addressed; potentialtoxicity issues ofnanoparticles regardingincineration, composting, orrecycling are unknown

exposure to elevatedtemperature and pressure;exposure to disulfide, sodiumhydroxide, isocyanates,volatile toxic, flammable, andmalodorous emissions ofsulfur, as well as tonanoparticles

Reprinted with permission from Ref. 35. # 2012, Elsevier. GMOs: genetically modified organisms;GHG: greenhouse gases.


Table 8. Environmental Impacts of BioplasticsQ1

Production stage Environmental impacts

feedstock new demand for biomass inputs can expand uses ofland, fossil fuels, chemical inputs, and water

feedstock choices can reinforce existing problemsassociated with corn and sugarcane; convertingforests or glasslands to expand agriculturalproduction can offset the CO2 sequestered byplants before harvest (Searchinger et al., 2008)

manufacturing and processing bioconversion is energy intensive (Gallezot, 2010)bioconversion may require the use of potentiallytoxic petroleum-based solvents (Ahman andDorgan, 2007) bioconversion produces significantwater effluent needing treatment (Ahman andDorgan, 2007)

bioconversion consumes water resources forfermentation, cooling, and heating

end-of-life fate compostable bioplastics may contaminate recycledplastic streams unless they are properly separatedand managed (Song et al., 2009)

compostable plastics require high temperatures todecompose in a landfill and special industrialequipment to be composted (Song et al., 2009)

unless a landfill is managed well and kept dry,degrading bioplastics will release methane gas

life cycle assessments significant reductions of energy consumption andGHG emissions are possible (McKone et al.,20111; Akiyama et al., 2003); conversely, PHAsand PHBs have higher GHG emissions because offossil fuel use for fertilizer production,agricultural production, corn wet milling,fermentation, polymer purification, and otherproduction processes (Kurdikar et al., 2001)

Reprinted with permission from Ref. 24. # 2013, Elsevier.

Table 9. Comparisonof aBioplastic (PHB)with aConventional Commodity Polymer (PP)

Impact category Unit PHB PP

abiotic depletion kg Sbeq 21.8 41.4global warming (GWP100) kg CO2eq 1960 3530ozone layer depletion (ODP) kg CFC-11eq 0.00017 0.000862human toxicity kg 1,4-DBeq 857 1870fresh water aquatic ecotoxicity kg 1,4-DBeq 106 234marine aquatic ecotoxicity kg 1,4-DBeq 1,290,000 1,850,000terrestrial ecotoxicity kg 1,4-DBeq 8.98 44photochemical oxidation kg C2H2 0.78 1.7acidification kg SO2eq 24.9 48.8eutrophication kg PO4

3�eq 5.19 5.84

Source: Ref. 36. LCIA of polymer production for 1000kg of polymer product—CML 2 Baseline 2000V2.03. Key: Underlined bold values are the lowest values in each category. Values in bold print arewithin 50% of the lowest value in each category.


compounds can contain nondegradable additives, and copolymers nondegradablemoieties). Biomineralization is a process generally concomitant to biodegradation,biofragmentation, and bioerosion. Specific modes are ‘‘hydrodegradation’’ orhydrolysis (by the action of water), photodegradation (by visible or ultravioletlight), oxidative degradation (by the action of oxygen) or photooxidative degrada-tion (by the combined action of light and oxygen), thermal degradation (by theaction of heat), thermochemical degradation (by the combined effect of heat andchemical agents), and thermooxidative degradation (by the combined action ofheat and oxygen). One can distinguish between physical and chemical degrada-tion. Biodegradation is cell mediated (eg, bacteria). Enzymatic degradation is aresult from the action of enzymes.

An environmentally degradable polymer is a polymer that can be degradedby the action of the environment, through, for example, air, light, heat, ormicroorganisms.

Depolymerization can be caused by the enzyme depolymerase. This term is tobe used when monomers are recovered (! feedstock recycling).

Deterioration, which can stem from physical and/or chemical influences, isthe deleterious alteration of a plastic material in quality.

Erosion is a degradation process that occurs at the surface and progressesfrom there into the bulk.

Fragmentation is the breakdown of a polymeric material into particlesirrespective of the mechanism and the size of fragments.

Mineralization is the process through which an organic substance is con-verted into inorganic substances (CO2, H2O, and other inorganics).

Composting is the decomposition of organic wastes by fermentation. It can beperformed industrially under aerobic or anaerobic conditions.

Biodegradable plastics must undergo degradation resulting from the actionof naturally occurring microorganisms such as bacteria.

Compostable plastics must further meet the following two requirements:

� They must biodegrade at a rate comparable to common compostable organicmaterials.

� They must disintegrate fully and leave no large fragments or toxic residue.

In short, a biodegradable plastic cannot be called compostable if it breaksdown too slowly, or if it leaves toxic residue or distinguishable fragments. Ingeneral, an increase in the hydrophobic character, the macromolecular weight,the crystallinity, or the size of spherulites decreases biodegradability (40). Thehigher the amount of natural polymers such as polysaccharides in blends, thefaster the degradation progresses. Such blends are, however, not completelydegraded; the bulkmaterial will be rendered into minute particles of conventionalpolymer, which are no longer visible to the naked eye like litter, but are stillpresent. An example is mulch film made from PE with starch as filler. Suchmaterials are generally no longer used (41).

Ideally, plastics aremineralized, ie, broken down and converted to water andcarbon dioxide after their use, which is mostly time limited. When a mineraliza-tion product is CH4, which has a high greenhouse warming potential (31), theenvironmental impact is significantly aggravated.


Degradation can occur by physical, chemical, and biological means. However,plastics were initially selected for their resistance to degradation in the environ-ment (bioresistant polymers). They withstand attack by microorganisms. Theirbiostability is associated with the following problems:

� Littering (visible contamination).

� Release of water-soluble and water-dispersed macromolecular compoundsand additives contained in the plastic products.

Somemodes 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 intendedto enhance their degradability (42,43).

For instance, BASF has been on the market for a decade with a compostablebioplastic made from fossil sources (Ecoflex) and one made from renewablesources (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 ofyears. In ancient times, natural plant gum was deployed to join pieces of wood inhouse building, and natural plant gum was applied as a waterproof coating toboats (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 elasticball. Starch has been used for centuries as glue for paper and wood and as gum forthe textile industry (47).

Table 10. Biodegradable Polymers

Biodegradable polymers from renewableresources

Biodegradable polymers from petroleumsources

polylactidepolyhydroxyalkanoates, eg, poly(3-hydroxybutyrate)

thermoplastic starchcellulosechitosanproteins

aliphatic polyesters and copolyesters (eg,polybutylene succinate and poly(butylenesuccinate-co-adipate))

aromatic copolyesters (eg, poly(butyleneadipate-co-terephthalate))

poly(3-caprolactone)polyesteramidespolyvinyl alcohol

Source: Ref. 45. For details on compostability of plastics, see Ref. 45.


The first plastics in the modern sense were produced in the end of 19th andbeginning of 20th century. Celluloid and cellophane were the first ones, and theywere biobased.

Natural rubber was originally derived from latex, a milky colloidal suspen-sion found in special trees. Its first use was cloth waterproofed with unvulcanizedlatex from Brazilian rubber trees.

In 1839, Charles Goodyear discovered vulcanization of natural rubbermaterials with sulfur for improving elasticity and durability. He also inventedEbonite (1852), a very hard rubber.

The first man-made plastic was Parkesine (1856), which was obtained fromcellulose treated with nitric acid. Bakelite, the first fully synthetic thermoset, wasinvented in 1907. The material, polyoxybenzylmethylenglycolanhydride, isobtained in an elimination reaction of phenol with formaldehyde. Another earlybioplastic, casein, was produced from milk proteins and lye. Casein, a family ofrelated phosphoproteins, is still used today for paints, glues, and in cheesemaking.Galalith (invented around 1897) is a synthetic plastic material manufacturedfrom casein and formaldehyde. Galalith was used for buttons around 1930.

In 1941, Henry Ford presented the ‘‘soybean car,’’ a plastic-bodied car shownat Dearborn Days, an annual community festival. It was 1000 lb lighter than asteel car; probably, the composition was ‘‘soybean fiber in a phenolic resin withformaldehyde 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 madepossible the mass production of these petrochemical polymers, and bioplasticsvirtually disappeared (compare the case of fuels, where biobased fuels that wereinitially used for combustion were replaced by petrol and diesel).

Modern bioplastics started emerging in the 1980s, when people wanted toreduce the volume of waste in landfills. They hoped that degradable plasticsdiscarded into landfills would take up less space once decomposed. This concept,however, failed, because landfills are sealed and oxygen, water, and sunlight arehardly available to break down the material.

Another concept that helped revive the interest in bioplastics was to reducethe use of petrochemicals for plastics production, as the price of crude oil becameunstable and started to rise (see oil crises of the 1970s). The first biopolymers wereblends of starch with conventional polymers, so that a certain biodegradabilityand use of natural feedstock were partly achieved.

Packaging, an area where plastic products have a short useful life, iscurrently one of the biggest markets for biopolymers, such as biodegradableplastic bags, compostable waste collection bags, and biodegradable or compostablefood 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 toslow sector maturation’’ after having invested an estimated $750 million (49). In2012, bioplastics company Metabolix reduced its production capacity of PHA from50,000 to 10,000 ton/yr (1), as sales volumes were too low at that time. Othermanufacturers have been successful in mass producing bioplastics, eg, Brazil’sBraskem (biobased PE made from sugarcane) or US NatureWorks (PLA).


6. Bioplastics by Genetic Engineering

Genetically modified organisms (GMOs) are extensively used in biotechnology.For instance, 80% of the >255 million tons of soybeans harvested annually aregenetically modified (50). Genetically engineered plants (51) and bacteria (52) alsoshow a good potential for bioplastics. Table 11 depicts several ‘‘phytofactories’’ forbiopolymers.

Transgenic means that the organism has received an exogenous gene, a so-called transgene, so that it exhibits and transmits to its offspring new properties.

Apart from bacteria, also (transgenic) plants can be used to produce bio-polymers such as PHA (53) (see Fig. 4).

7. Description of Important Bioplastics

At present, the biggest market share among biodegradable bioplastics is held byTPS and blends made thereof, accounting for approximately 60% of consumption(54). Next in line is PLA with approximately 20% market share, followed by CAwith 15% market share. Other bioplastics such as PHAs are at a market sharebelow 5%, at present. It is assumed that PLA is growing fastest (54).

Figure 5 shows an overview of biodegradable plastics in four families. Anextensive list of bioplastics is provided in Reference 6.

Biobased polyethylene is the most common nondegradable biopolymer.Below, important biobased plastics are described. First, drop-in replacements(PE, PP, PVC, and PC) will be discussed, followed by biodegradable biopolymers.Note that also blends containing biobased plastics are manufactured. Drop-inbioplastics are chemically identical to their petrochemical counterparts, but theyare at least partially derived from biomass. Generally, one can see a trend towardthe replacement of conventional petroplastics by these drop-in solutions, withbiodegradable bioplastics receiving comparatively less attention (55). Statisticsfrom European Bioplastics show that durables accounted for almost 40% ofbioplastics in 2011, up from around 12% in 2010 (19). This trend is in linewith improving properties of bioplastic formulations.

7.1. Biobased PE. PE is one of the most widely used commodity thermo-plastics, eg, for packaging (plastic bags, plastic films, geomembranes, and con-tainers including bottles). Variants are HDPE, LLDPE, and LDPE (high densityPE, linear low density PE, and low density PE, respectively). The monomer,ethylene, is commonlymade from crude oil (via cracking), natural gas, or shale gas(from NGLs (natural gas liquids) (56) or methane after dimerization (57)). Bio-based PE was first commercialized by Brazilian company Braskem utilizing localsugarcane-derived ethanol/ethylene as feedstock. In September 2010, Braskemstarted commercial production of biobased HDPE with a capacity of 200,000 ton/yr. The material’s composition and performance are comparable to those ofpetroleum-based PE. According to ICIS (1), the ‘‘green PE’’ has a price premiumof around 15–20%, which is possible in selectedmarkets and covers the higher costof production compared with petrochemical-based plastics. Another bio-PE plantwas built in Brazil by Dow Chemical and Mitsui. That plant has a capacity of350,000 ton/yr with main target markets in flexible packaging, hygiene, and


Table

11.

NovelBiopolymers

Producedin

Transgenic

Plants

Polymer

Nativeproductionhost

Structure

Plantmetaboliteusedfor

synthesis

Properties/application

s

PHAs

bacteria;producedasa

carbon

anden

ergy

storagepolymer

under

nutrientlimiting

growth

conditions(55)

�hom

opolymersand

copolymersof

polymerized

hydroxy

acids

�PHBmostcommon

target

inplants

dep

endson

polymer

composition

�PHB:acetyl-CoA

oracetoacetyl-CoA

�PHAMCL:fattyacids

�PHBV:acetyl-CoA

and

threon

ine

�dep

endson

polymer

composition

�application

sin

plastics,

chem

icals,andfeed

supplemen

ts

spider

silk

spiders;producedfor

web

sandwrappingof

prey

fibrousproteinswith

repetitivesequen

ces

possessingmany

non

polarand

hydrophob

icamino

acids

aminoacids

�multiple

types

ofprotein

silk

fibersex

istthatpossess

differentproperties

(41,56)

�goo

delasticityandtensile

strength

�clothing,textiles,med

icaluses

elastin

mammals;ex

tracellular

matrix

protein

providingmechanical

integrity

totissues

fibrousproteinswith

repetitiveamino

acidsequen

ces

aminoacids

�tissueen

ginee

ring,gels,fibers,

scaffolds(57);soluble

derivatives

ofelastin

(ie,

trop

oelastin

andelastin

pep

tides(E

LPs))havemore

usefulproperties

andthus

broader

application

s(57)

�fusion

ofELPsto

other

proteins

canincrea

seprotein

production

(44)

collagen

anim

als;protein

foundin

connectivetissue

fibrousproteins

aminoacids

med

icalapplication

sincluding

tissueen

ginee

ring,su

rgical

implants,anddru

gdelivery

(58)

cyanop

hycin

cyanob

acteria

andother

photosynthetic

and

non

photosynthetic

bacteria;producedas

nitrogen

storage

compou

nd

non

ribosom

ally

producedaminoacid

polymer

ofasp

artic

acidback

bon

eand

argininesidegroups

asp

artic

acidand

arginine

�productionof

polyasp

artate,a

polymer

withapplication

sin

superadsorben

ts,after

chem

icalhydrolysisof

arginine

�precu

rsor

fortheproductionof

chem

icals

(2)

Sou

rce:

Ref.53.PHB,poly[(R)-3-hydroxybutyrate];

PHAMCL,med

ium

chain

length

PHA;PHBV,copolymer

of(R

)-3-hydroxybutyrate

and

(R)-3-

hydroxyvalerate.

18

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 inplants has the potential to provide a renewable cheap source of polymeric material that canbe used for the production of plastics, chemicals, and feed supplements with lignocellulosicor seed oil coproducts that can be used to produce energy. Transmission electron micro-graphs from thin sections of switchgrass leaf tissue and Camelinamature seeds are shownin the insets and illustrate the accumulation of PHB in the form of granules in a bundlesheath 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.)


medical applications. Since the project covers the entire value chain from growingsugarcane to producing the biopolymer (1), it is competitive to conventionalpolymer production.

7.2. Biobased PP. Polypropylene, the second most common commodityplastic, can likewise be made from renewably sourced feedstock. Propylene isaccessible from methane via ethylene dimerization followed by metathesis (58).Braskem has announced plans to build a 30,000–50,000 ton/yr biobased PPproduction 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 thirdmost common thermoplastic is PET. It is athermoplastic polymer resin of the polyester family. It is mainly used for syntheticfibers (then called ‘‘polyester’’) and for packaging, primarily bottles. Themonomerethylene terephthalate (bis(2-hydroxyethyl) terephthalate) can be synthesized byesterification between terephthalic acid and ethylene glycol, or by transesterifi-cation between dimethyl terephthalate with ethylene glycol. Polymerization isdone through a polycondensation reaction of the monomers, carried out immedi-ately after esterification/transesterification. Biobased PET can contain renewablemonoethylene glycol (MEG), produced, eg, from sugarcane-derived ethylene, asbeing promoted by Coca Cola under the name Plantbottle (60,61). Its competitorPepsi 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 fullybiobased alternative. Plantbottle PET is produced from terephthalic acid (70% bymass) and ethylene glycol (30% by mass), the latter coming from renewableethanol. The formulation is also termed Bio-PET 30. An alternative to PET isthe bioplastic polyethylene furanoate (PEF), which is expected to become com-mercially available as of 2016 (63). The bacteria Nocardia can degrade PET withits 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 specialenvironmental challenges, eg, phthalates, so the material’s reputation is not sohigh. 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 tocreate biobased plasticizers for the replacement of phthalates. There are over 300known plasticizers, with 50–100 being used commercially (65).

7.5. Biobased PC. Polycarbonates are situated between commodityplastics and engineering plastics, as they exhibit an interesting combination oftemperature resistance, impact resistance, and optical properties. Conventionalpolycarbonate is made from toxic monomers, bisphenol A (BPA), and phosgene(COCl2).

An alternative polycarbonate can partly be made from isosorbide (derivedfrom glucose: hydrogenation of glucose gives sorbitol, and isosorbide is obtained bydouble dehydration of sorbitol): Companies Mitsubishi and Roquette haveannounced pilot plants for making isosorbide and incorporating it into PC (66).Manufacturing PC from isosorbide and a diaryl carbonate removes the need to usephosgene and bisphenol A in the process (1). The biobased PC is seen as still farfrom commercialization (1). In Reference 67, the potential of a derivative ofcashew nutshell liquid (CNSL) as an alternative to BPA is discussed.


7.6. Biobased PU. Polyurethanes (PU, RPUR, and BUR) are thermo-setting polymers commonly formed by reacting a di- or polyisocyanate with apolyol. Applications are rigid foams. The polyols can be obtained from plant oil tomake a biobased PU. Natural oil polyols (NOPs, biopolyols) (68) are derived fromvegetable 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, orsoybean oil need to be treated to introduce ��OH groups, mainly by double bondoxidation.

7.7. Cellulose Acetate. Cellulose esters are another important group ofbioplastics. The most common cellulose esters comprise CA, cellulose acetatepropionate (CAP), and cellulose acetate butyrate (CAB). They are thermoplasticmaterials produced through esterification of cellulose (45). Applications aresynthetic fibers, cigarette filters, and formerly photography film.

7.8. Polylactic Acid. Polylactic acid or polylactate is obtained from themonomer lactic acid, which is produced from the microorganism-catalyzedfermentation of sugar or starch. It is similar in properties to PET and hasFDA approval for food contact. Common raw materials are corn starch, sugar-cane, and tapioca (starch extracted from cassava root). Chemically, PLA is not apolyacid (polyelectrolyte), but rather a polyester. Companies active in the fieldare, eg, NatureWorks, Purac, and Teijin (1). PLA is used for yogurt cups, whereit replaces polystyrene. Due to inferior material properties (heat resistance,impact resistance, and low glass transition temperature), PLA is often blendedwith conventional petroplastics. Costs of PLA have improved over the lastdecade and are expected to go down further as capacity is added, eg, byNatureWorks (140,000 ton/yr) and Purac (750,000 ton/yr) (1). NatureWorks’Ingeo is manufactured in a two-step process that starts with fermenting thedextrose derived from hydrolysis of corn starch. The product of the dextrosefermentation, lactic acid, is further treated to create the intermediary monomerlactide (the cyclic diester of lactic acid), which is then polymerized throughopening polymerization (39).

Polylactic acid and its copolymers can also be obtained from engineeredEscherichia coli (69).

Composite materials of PLA, eg, with woven bamboo fabric, have beenreported (70).

PLA is subject to abiotic degradation (ie, simple hydrolysis of the ester bondswithout requiring the presence of enzymes). It is also biocompatible.

Monomer stereochemistry (D- and L-lactic acid) can be controlled to imparttargeted utility in the final polymers (71), by the relative contents of bothhomopolymers (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. PLAhas a strong potential for future use, spearheading bioplastics proliferation, sinceit 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 isdescribed in Reference 48. For details on PLA, see References 46 and [74]74–76 forapplications.


7.9. Polyhydroxyalkanoates. PHAs (77–82) are a wide group of bio-polymers, but mostly refer to poly(3-hydroxybutyrate) and its copolymer PHBV(poly(3-hydroxybutyrate-co-3-hydroxyvalerate)); see Figure 7 for the generalstructures.

These polyoxoesters are produced by bacteria from sugar or lipids throughpolyhydroxy fatty acids from anaerobic digestion. PHAs are an intracellular(energy storage) product of the bacteria (see Fig. 8).

Approximately 250 different bacteria were found to produce PHA. Thebioplastics are then harvested through the destruction of the bacteria and are

Fig. 6. Biodegradation of a disposable cup made from PLA. Time sequence: 1, 15, and30 days (top); 45 and 58 days (bottom). (Source: Reference 73.)

Fig. 7. The general structure of polyhydroxyalkanoates. (Source: Reference 83.)


separated from the microbial cell matter (centrifugation/filtration and PHAextraction using solvents such as chloroform).

PHAs have good barrier properties and, since they are biodegradable (85),are attractive for biomedical uses (1,39). PHA can also meet ASTM D7081, whichis the standard specification for marine degradability (39).

The main attributes of PHAs are as follows:

� Fully biodegradable in soil, water, and compost.

� Good printability.

� Good resistance to grease and oils.

� Can withstand boiling water (HDT >120�C).

Most commercial products are injection molding grades. PHAs are sold, eg,by company Metabolix. Issues that limit commercialization of PHA are theirbrittleness, a narrow processing window, a slow crystallization rate, and sensi-tivity to thermal degradation (1). Similar to PLA, material shortcomings canpartly be overcome by blending with additives and other polymers. PHB is similarin 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).

Fig. 8. Transmission electron microscope images: microbial cells containing native PHBgranules (a), cells with damaged walls in acid pretreatment (b), PHB granules withattached residual cell mass (c), and purified PHB granules (d) (Source: Reference 84.)


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. Thedegrading microbes colonize the polymer surface and secrete PHA depolymerases.Reactions are as follows:

PHA ! CO2 þH2O ðaerobicallyÞPHA ! CO2 þH2Oþ CH4 ðanaerobicallyÞ

Reactive extrusion can be used for grafting functional groups onto the PHAbackbone 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 madefrom succinic acid and 1,4-butanediol (BDO). Companies active in the field are, eg,BioAmber, Reverdia, Myriant, and Purac (1).

7.11. Polyvinyl Alcohol. Polyvinyl alcohol (PVOH, PVA) is a bio-degradable water-soluble polymer (97).

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 39.90xylose 13.408 5.02 37.44sucrose 9.316 4.97 53.35rhamnose 9.402 5.01 53.28mannitol 9.942 5.00 50.29maltose 8.636 4.88 56.51lactose 8.502 5.06 59.52mannose 9.114 4.97 54.53galactose 15.494 4.92 31.75starch 17.312 5.05 29.17raffinose 8.37 5.07 60.57

Source: Ref. 86.

Table 12. Physical Properties of Various PHAs and PP

Property PHBP(HB-HN)

Polypropylene3 mol% 14 mol% 25 mol%

melting point, �C 175 169 150 137 176glass transition temperature (�C) 15 – – �1 �10crystalline, % 80 – – 40 70Young’s modulus 3.5 2.9 1.5 0.7 1.7tensile strength, MPa 40 38 35 30 34.5elongation to break, % 6 – – – 400impact strength, V/m 50 60 120 400 45

Source: Ref. 83.


7.12. Biobased Polyethylene oxide. Polyethylene glycol (PEG) is apolyether compound with the formula H��(O��CH2��CH2)n��OH. It is soluble inwater.

PEG is also known as polyethylene oxide (PEO) or polyoxyethylene (POE),depending on molecular mass. All are oligomers of the monomer ethylene oxide.Generally, PEG is used for oligomers and polymers with a molecular mass below20,000 g/mol and PEO for polymers with a molecular mass above 20,000 g/mol.The expression POE is used for a polymer of any molecular mass. PEG hasnumerous applications in industry and medicine.

7.13. Biobased Polyamide. Polyamides are macromolecules withrepeating units linked by amide bonds. They occur naturally and artificially.Examples of the former are proteins, such as wool and silk. Synthetic polyamidesare often used in textiles and the transportation industry. Two common PAs arethe homopolymers PA 6 ([N��H��(CH2)5��CO]nmade from e-caprolactam) and PA66 ([NH��(CH2)6��NH��CO��(CH2)4��CO]n made from hexamethylenediamineand adipic acid).

Rilsan is a commercially available biobased polyamide (PA 11) made fromcastor oil (sebacic acid).

7.14. Chitosan. Chitosan is a form of chitin, one of the most abundantorganicmaterial on Earth. Chitin is a tough polysaccharide found, eg, in the shellsof shrimp and other crustaceans. The development of chitosan-based bioplastics isstill in the beginning (98–100).

7.15. Thermoplastic Starch. Starch is the major carbohydrate energystorage product of plants. The group of polysaccharides is the most abundantbiopolymer group on Earth. Starch is also cheap. It can even be sourced fromwastes such as defatted cashew nut shells (101).

Concerning biopolymers, there are several options. First, starch can beconverted into chemicals such as ethanol and organic acids, from which syntheticpolymers can be made. Second, it can be used as filler in plastics. Third, modifi-cation of the starch, eg, by grafting, is possible.

The first attempts to use starch in bioplastics were made in the 1970s (41).Sorbitol and glycerol can be used to plasticize the starch into a plastic.

When blending starch with thermoplastic polymers (petro-derived or bio-based), thermoplastic starch, which is biodegradable (biodisintegrable), isobtained. It was invented in 1988 (EP 0397819). One of the largest thermoplasticstarch producers is Novamont with its product MaterBi, which has been on themarket for two decades (39).

Apart from films, bags, and small appliances such as ballpoint pens andcutlery, expanded packages (foams) can be made from TPS, where properties arecomparable to EPS and XPS foam (41) (see Fig. 9).

TPS is, eg, marketed as Plastarch Material (PSM) made from corn starch.For details on TPS, see References 41, 47, 103, and 104.

7.16. Cellophane. Cellophane is a thin, transparent sheet made ofregenerated cellulose, a glucose polymer. The cellulose from, eg, wood, cotton,or hemp is dissolved in alkali and CS2 to produce viscose, from which a fiber(rayon) or a film (cellophane) can be made in a bath of sulfuric acid and sodiumsulfate. It was invented around 1930 and amply used; however, due to the use ofCS2 in manufacturing, its importance declined, although the material itself is


biodegradable. Cellophane is used for food packaging and also to wrap cigars, as itallows them to ‘‘breathe’’ (the material is permeable to moisture). Note that theterm ‘‘cellophane’’ has become genericized, so it is often used informally to referplastic film products of other materials, too.

7.17. Polyesteramides. Polyesteramides (PEAs) are bioabsorbable. Theycan also be made from renewable resources. For details, see Reference 105.

7.18. Alginate. Alginate (alginic acid, algin) is a polysaccharide acquiredfrom the cell walls of brown algae. Alginate has been exploited for a long time as apolyelectrolyte material (99). It can absorb 200–300 times its ownweight 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 verylow melting point of around 60�C. The most common use of polycaprolactone is inthe manufacture of speciality polyurethanes. Biomedical applications includesurgical suture.

Its physical properties make it a very tough, polyamide-like plastic thatmelts to a consistency like putty at only 60�C. This makes PCL attractive for thehobbyist 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 thermoplasticsarea (107). PTT is made from 1,3-propanediol (PDO), which can be obtained viaseveral renewable routes, eg, by aerobic fermentation from glycerol or glucose.The bioprocess of PDO production was found to consume 40% less energy and tocut 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-degradable, thermoplastic polymer. It constitutes the simplest linear, aliphatic

Fig. 9. Extruded starch foam. (Reprinted with permission from Reference 102. # 2015,Elsevier.)


polyester. The glycolic acid is derived from glucose, eg, from sugar beets, andglycolic 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, asEcovio.

7.23. Other Bioplastics. There are significantly more bioplastics underinvestigation 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 thescope of this article. For soy protein plastic (SPP) and sugar beet pulp (SBP)plastics and composites, see Reference 110. For further bioplastics, see References6, 111, and 112.

8. Biobased Additives

As mentioned earlier, plastics are composed of polymers and additives, whichenhance performance. Additives can be organic or inorganic. Examples includemineral fillers, UV stabilizers, color pigments, flame retardants, processing aids,and plasticizers.

Several additives are problematic, eg, toxic compounds, heavy metals, andleaching/migrating additives. Conventionally produced organic additives can alsobe replaced by renewable ones.

Examples are as follows:

� 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 forpigments and UV stabilizers (115).

Industry initiatives are reported in References 116 and 117.Formore information on biobased additives, see, eg, Reference 118.Biobased

fibers (eg, hemp) and fillers (eg, rubberwood flour) for composite materials are outof the scope of this article.

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.


The recycling industry has created a recycling code system from 1 to 7 forplastics. The higher the number, the more difficult it is to deploy the materialprofitably 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, whilethe latter aims at recycling themonomers. A variant is dry-heat depolymerization.

Waste treatment of bioplastics has been an active field of research; seeFigure 13 for the frequency of patent applications. Most of these patents are filedin Japan and the United States.

Fig. 11. Resin identification codes (RICs) for physical recycling. Bioplastics all fall under 7.

Fig. 10. Options for disposal of bioplastics. (Source: Reference 6.)


10. Labeling and Certification

Bioplastic products on the market today are found in many conventionalapplications alongside ‘‘standard’’ plastics, eg, bottles, cutlery, packaging goods(bags), carpets, textiles, plates, and films. They are (partly) made from a varietyof feedstocks including sugarcane, corn, rice, potatoes, cellulose, bagasse, and

Fig. 13. Patent applications on biopolymers and their waste treatment worldwide duringthe period January 1, 1990 through August 31, 2012. (Source: Reference 6.)

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.)


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 validateclaims (119).

Ambiguous and competing terminology is used in marketing; see Figure 14as an example.

In the United States, the Federal Trade Commission controls environmentalclaims in the U.S. Code of Federal Regulations (CFR) Section 16, Part 260 (16 CFR260)—Guides for the Use of Environmental Marketing Claims. Similar provisionsexist in other countries.

Clear labeling and certification can help distinguish between conventionaland biobased plastics. Labels to indicate a certain product quality are wellestablished on the consumer market, eg, for organic food, energy efficiency,and fair trade.

Independent and internationally respected labels provide transparent andaccurate information for customers, and they help maintain a good reputation ofthe bioplastics industry. Ideally, labels are linked to a recognized standard.

Currently, several (voluntary) certification systems exist worldwide withregard to compostability, eg, DIN CERTCO, VinScotte and European Bioplastics(Europe), BPI (USA), JBPA (Japan), and ABA (Australia). These systems are allbased on the same international standards (EN 13432, ASTM D6400, and ISO17088) with similar requirements, but nevertheless show some minor and some-timesQ2 . In the United States, the percentage of biobased ingredients required for a

Fig. 14. Competing terminology: ‘‘100% COMPOSTABLEBAG,’’ ‘‘100% COMPOSTABLE,’’‘‘100% BIODEGRADABLE,’’ and ‘‘BIODEGRADABLE PLASTIC.’’ (Source: Reference 39.)


product to be referred to as biobased is defined by the USDA (United StatesDepartment of Agriculture) on a product-by-product basis (120). ILSR (Institutefor Local Self-Reliance) has recommended that a minimum of 50% biobasedcontent for products to be considered biobased (120).

The organic carbon in a product can be assessed according to CEN/TS 16137and ASTM D6866. Sometimes, biobased mass content is also used.

In the United States, the U.S. Composting Council worked with the Bio-degradable Products Institute (BPI) (121) to establish a labeling program tocertify compostable products.

Certification can concern compostability and/or a renewable feedstock base.Commonly used logos for compostability are shown in Figure 15.

ASTM D6400 and EN 13432 demand ‘‘84 days disintegration; 180 daysmineralization.’’ Additional requirements include limits for the content of heavymetals, ecotoxicity analysis, and the level of compost quality, which is determinedby a plant growth test.

Strategies for the promotion of biodegradability and the suppression ofbiodegradability are discussed in Reference 6. The lifetime of bioplastics can beextended by cross-linking, blending, additivation, coatings, surface modification,and the removal of impurities. Ideally, the lifetime of bioplastics is tailored to thespecific application.

11. Current Applications of Bioplastics

The use of bioplastics is as diverse as that of conventional plastics.Below, several prominent applications of bioplastics are highlighted. For

images, see, eg, Reference 122. Due to the ample usage options, this compilationcannot be complete.

Out of scope of this article are particularly biopolymers in controlled-releasedelivery systems (124) and tissue engineering. Lignosulfonates, humic acids,waxes, plant oils, xanthane, and proteins (eg, collagen, gelatin, keratin, wool,and silk) are also not covered, as they are biopolymers of technical use, but notplastics.

Fig. 15. Compostability logos used in different countries. (Source: References 122 and 123.)


Poultry feathers, which contain over 90% keratin, and of which >4 billionpounds are generated in the U.S. poultry industry each year alone, have beenenvisioned for bioplastics production (125), as fiber filler. As shown in Figure 16,the main applications for bioplastics are seen in packaging, the automotiveindustry, and agriculture.

11.1. Packaging. In the plastics industry today, there is no largermarketsegment than packaging, which consumes approximately 100 millions tons ofmaterials 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, isto cover seeded areas in order to protect the growing plants from weeds and lowtemperatures, 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 nottotally degradable.

11.3. Microbeads in Cosmetics. Plastic waste that ends up in theoceans is fragmented into small particles called ‘‘microplastics.’’ Fish and birdsthat take it for food eat these particles and inflict damage. Apart from containingand releasing toxic products, microplastics were found to act as concentrators fortoxins (126) and persistent organic pollutants (POPs) (127). The microplasticsbecome enriched in the food chain and end up on humans’ plates (126). Also, smallpolyester fibers from washing operations end in the environment. On top, severalcosmetics such as facial scrubs, toothpastes, and shower gels deliberately containmicrobeads of plastics. These microexfoliants serve the purpose of peeling. Theyare too small to be filtered by sewage treatment plants. Biodegradable alterna-tives are, eg, alginate, chitosan, and gelatin microbeads (128).

Fig. 16. Markets for bioplastics (2012 data). (Source: Reference 8.)


11.4. Automotive Industry. The automotive industry is taking initia-tives toward sustainability, including attempts to utilize bioplastics. Due to thelarge number of vehicles manufactured, the impact can be big. According toRenault, more than 500 different plastic parts are typically deployed in an averageEuropean car, eg, for bumper, fender, instrument panels, trims, headlamp, airintake manifold, fuel tanks, etc, and several plastics are used (PP, PA, HDPE,ABS, PC, POM, PBT, etc)

Examples of bioplastics in cars are as follows.Toyota claims to have been the first car manufacturer to use sugarcane-

based PET in vehicle liners and some interior surfaces. The company aims to have20% of all plastic components in its vehicles made of bioplastics by 2015 (129). Fiathas used castor oil-derived polyamides and soybean-derived polyurethanes for carparts (129).

Seventy-five percent of Ford vehicles produced annually contain soybean-based foam in headrests (129)

Mazda Motors Corp. claims a plant-derived content above 80% in interiorfittings in one model, plus a 100% plant-derived biofabric for seat covers (129).

For details, see Reference 130.

12. Challenges with Bioplastics

Brand owners seek solutions for a ‘‘green,’’ ‘‘eco-friendly’’ image, speaking aboutcorporate social responsibility (CSR), and consumers are looking for sustainable—yet cost-effective—products. The development and widespread acceptance andproliferation of bioplastics have to face several challenges. Today, bioplastics canbe considered to be in their infancy, yet there is significant potential. In the nearterm, blending with polyolefins and other petrobased plastics is a viable approachto start using them, contributing to sustainability, while concurrently working toimprove 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 isreally superior to that of conventional plastics. The following aspects have to beconsidered:

Composting: Often, bioplastics can only be composted in industrial, hightemperature composting facilities, which is generally positive; however, itlimits the use of, eg, bioplastic bags for home composting, and bioplastic litterwill still be visible.

Recycling: Bioplastics are generally not accepted for recycling with standardplastics, so mixed collections pose a problem. For instance, a small fraction ofPHB in PET can render the recycled material useless for high valueapplications. Dedicated infrastructure for bioplastics collection will be nec-essary, which is not in place yet. While single use of neither petroplastics norbioplastics is desired, concern over contamination of recycling streams is amajor barrier in bioplastics acceptance. For details on bioplastics recycling,see, eg, Reference 6 and the next section.


Performance: The density of bioplastics is generally higher than that ofpolyolefins(1.2–1.3 g/cm3 vs 0.9 g/cm3). Used in cars, bioplastics mean more weight,resulting in higher fuel consumption, for instance.

Costs: Generally, bioplastics are more expensive than petrobased plastics.Figure 17 shows the typical contribution to production costs for PLAmanufacturing from raw materials (>3/4), investments, utilities, andlabor.

Also for bioplastics, economies of scale apply, so pilot plants cannot compete withestablished, large petroplastics plants, and new commercial bioplastics plants aretypically smaller than petrochemical ones.

Material and processing knowledge: Companies that manufacture plasticgoods from resins have less knowledge on the processing of bioplasticsthanwith conventional plastics, so they are hesitating to switch, particularlysince some bioplastics are more difficult to process (they require lowertemperatures, or putting it another way, damage to the material is incurredmore easily).

Sustainability of the feedstock: In case the feedstock is derived from food orgrown of valuable cropland, food prices might increase due to competition.Land use change can have an adverse effect on climate change; see also thediscussion about first-generation biofuels (aspects are large-scale monocrop-ping and the destruction of rainforests). Here, non-food feedstock, eg, cellu-lose or algae, could pose a solution. In case of lignocellulose (wood), twoschemes that certify sustainability production are FSC and PEFC.

Other concerns: These include the lack of adequate labeling/certification (seealso above), and, for instance, nanocomposites (20), which are used in somebioplastics (although they are deployed in conventional plastics, too). Someresearchers investigate genetically modified organisms (plants and bacteria)for bioplastics production, eg, feedstock (glucose, ethanol) or plastics (PHB),which also face acceptance concerns in the public.

Fig. 17. Cost split for a mid-sized PLA plant. (Source: Reference 131.)


13. Market Size of Bioplastics

Figure 18, showing data for 2012, estimates the global market size for bioplasticsto amount to 1.4 million ton/yr, which is roughly 0.5% of the total current marketfor (new) plastics.

One-third of global bioplastics ismanufactured in South America (2) (see Fig.19). Figure 19 also shows a projection for bioplastics market size in 2017. One cansee that the nonbiodegradable bioplastics will strongly increase, whereas bio-degradable plastics will see only moderate growth (see also Section 14).

Fig. 18. Market size for bioplastics. (a) Biobased vs biodegradable materials. (b) Split bymaterial. (Source: Reference 8.)

Fig. 19. Global bioplastics production (2012 data) by region (a) and type (b). (Source:European Bioplastics/University of Applied Sciences and Arts, Hanover (8).)


14. Market Outlook for Bioplastics

The growth in bioplastics is driven by the expansion in demand. One can observea shift from compostable (biodegradable) to durable bioplastics, away fromsingle-use applications such as disposable bags or plastic cutlery towardmore valuable, high performance goods such as automotive parts and householdappliances. 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 whichwas utilized—is expected to triple to nearly 12 million tons by 2020 (132).With an estimated total polymer production of roughly 400 million tons in2020, 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. BiobasedPET should reach a production capacity of about 5 million tons by the year2020, using bioethanol from sugarcane, followed by biobased polyolefins suchas PE and PP from the same feedstock. PLA and PHA are expected to atleast quadruple the capacity between 2011 and 2020. Most investment innew biobased polymer capacities is estimated to happen in Asia and SouthAmerica because of better access to feedstock. Europe’s share in bioplasticswill 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 from13 to 18%. This means that each region of the world will see an increase inbioplastics use (132).

15. Conclusions

The proliferation and use of bioplastics should not be determined by their relativecosts, but by their performance instead. Specific advantages for target applica-tions need to be worked out. Bioplastics are not generally more environmentallysound than conventional plastics. They can be based on renewable feedstock,biodegradable, or both. Bioplastics currently only constitute approximately 1% ofglobal plastics production; however, a huge potential is seen. Drop-in bioplasticshave identical properties to their petrochemical counterparts, which has acceler-ated their commercialization. ‘‘Green’’ PE and PET are already on the market, asare PLA and starch blends. With consumer consciousness and sustainabilitybecoming new market drivers, the push to bring more bioplastics to commerciali-zation has become stronger, improving properties and performance, and reducingproduction cost (1).

By finding suitable monomers from renewable feedstock, a cost-effectiveswap toward bioplastics is feasible, because no entirely new polymerization planthas to be built, but only the upstream infrastructure is amended, eg, by afermentation unit or a catalytic cracker. The concept of a biorefinery (133) alsofits well into bioplastics, several high value products can be obtained from a givenfeedstock/raw material mix, and integration brings costs down.


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MAXIMILIAN LACKNER

Vienna University of Technology, Vienna, Austria


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Keywords/Abstract

Dear Author,

Keywords and abstracts will not be included in the print version of your article but onlyin the online version. The abstract and keywords are included in the print version onlyfor your review.

Abstract:

Bioplastics are biobased polymers with two sustainability concepts: biodegradability andrenewability. On the one hand, bioplastics that biodegrade to CO2 and H2O in theenvironment can be produced, eg, avoiding litter and damage to marine organisms. On theother 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 theclimate. Currently, bioplastics have a market share of �1%, yet they experience annualgrowth rates in excess of 20–30%. This article highlights some key aspects associated withbioplastics, the performance of which can be tailored to meet that of petrochemicalpolymers or to offer new properties, eg, by blending and additivation. Importantbioplastics 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.

Keywords: Bioplastics; biobased polymers; sustainability; biodegradability;compostability.

Author Query

1. Please include the references cited in Table 8 in the reference list or else deletethem from the table body.

2. The intended meaning of the text ‘‘but nevertheless show some minor andsometimes’’ is not clear. Please check.

3. Please provide the name(s) of the assignee(s) in Reference 43.

Documents

BIOPLASTICS: BIOBASED PLASTICS AS … · BIOPLASTICS: BIOBASED PLASTICS AS RENEWABLE AND/OR BIODEGRADABLE ALTERNATIVES TO PETROPLASTICS 1. Introduction ‘‘Plastics’’ were introduced