State of Knowledge

2.1

History of Biopolymers

In the beginning of industrialization, the only polymer materials produced, such as cellulose
derivatives and rubber, were based on renewable resources (cf. (I.) in Fig. 2.1). Natural raw
materials were the only ones available in suitable quantities at that time. The successful
advance of petro-chemistry displaced renewable resources as polymer raw materials in favor
of petrochemical based raw materials (11.). Based on these petrochemical raw materials, the
first biologically degradable polymer materials, such as polyvinyl alcohols or polycaprolactone, were developed for certain niche applications (111.) in the last decades. Although
petrochemical based plastics provided unprecedented convenience in processing and use
properties, the dependency on limitedlforeign resources for raw materials and the negative
disposal properties led to a change in focus. Disposal or recycling potential of polymers
received more and more emphasis and an increasing number of degradable biopolymers
have been developed since the end of the 1980s, based mainly on renewable resources
(IV.) [20, 26, 271. Meanwhile, the expected shortage of resources and continuously rising
prices of petrochemical raw materials have shifted the main emphasis among biopolymer
materials. Compostability is no longer the main criterion, instead the use of renewable,
i. e., long-term available resources for manufacturing raw materials, has become the main
consideration (V.).

Figure 2.1 Historical developments of biopolymers

20

2.2

State of Knowledge

Development of Successive Biopolymer Materials

Generations

Interest in biopolymers /
Development of biopolymers

More than 30 years ago, i.e., in the late 1980s and early 1990s, innovative biopolymers especially those based on starch and polyhydroxyalkanoates manufactured by fermentation - were introduced to the market for the first time [19, 21, 22, 26, 27, 28, 291. Despite
certain euphoria and encouraging prognoses, these biologically degradable first generation
biopolymers could not be successfully established in the market, in particular because of their
yet untried material properties, unfavorable political and economical circumstances, as well
as a lack of political will among decision makers in industry and politics (Fig. 2.2).
Once the regulatory framework began to change, work began on the development and optimization of a wide variety of biopolymers in recent years. These improved second generation
biopolymer materials currently on the market are largely comparable with conventional bulk
plastics in terms of processing and use properties and increasingly competitive in certain
applications, e. g., as packaging materials [26,30,31, 32,331. Currently, these materials suffer
from minor economic disadvantages, due mainly to their still low production volume. This
will be compensated once disposal costs are taken into consideration and/or production
volumes have increased further.
Meanwhile, the manufacture of some of these second generation biopolymers has reached
industrial scale (Fig. 2.3). Some of the first plastics ever produced, regenerated cellulose
and cellulose derivates, are among the biopolymers already being manufactured on a large
industrial scale together with polycaprolactone and polyvinyl alcohol. Innovative biopolymer

Crude oil price record

($ 147.5 per barrel)

Hurricane
Katrina
Introduction of
packaging regulations

First biopolymer Second biopolymer

generation
generation

First Gulf War

1990

Third biopolymer generation

1995

2000

2005

2010

Figure 2.2 Changing, but constantly growing interest in biopolymers influenced by regulatory
developments

2.2

Development of Successive Biopolymer Materials Generations

21

PLA: Polylactide
PMMA: Polymethylenmethacrylat
POM: Polyoxymethylene
PP: Polypropylene
PTT: Polytrimethyleneterephthalate
PUR: Polyurethane
PVAL: Polyvinyl alcohol
PVC: Polyvinyl chloride

CA: Cellulose acetate

PA: Polyamide
PBS: Polybutylene succiate
PBSA: Polybutylene succinate adipate
PBT: Polybutylene terephthalate
PC: Polycarbonat
PCL: Polycaprolactone
PE: Polyethylene
PET: Polyethylene terephthalate
PHA: Polyhydroxyalkanoate

PBS, PBSA

Bio-PMMA

Bio-PA

Bio-PC

Bio-PET

Bio-PP

PBT

Bio-POM

Research

Development

PCL

Bio-PUR

Degradable
polyesters

Cellulose
regenerates

PHAs

Starch blends

CA

PTT

PLA

PVAL

Pilot Scale Commercial

Large Scale

Industrial

Figure 2.3 State of development (2010) of thermoplastic biopolymers [26]

materials such as polylactide, starch blends, and various polyesters are also already in largescale production.
These second generation biopolymers were developed almost exclusively as degradable and
compostable materials for the packaging, agriculture, or gardening sector. Now there are polymer materials for engineering applications based on these second generation biopolymers,
gaining in interest as they enter other fields, such as the automotive and textile industries.
The trend among the third generation biopolymer materials is away from degradability and
toward resistance. At the same time, in view of limited petrochemical raw materials supply, the use of renewable resources for the manufacturing of materials is gaining traction.
Long-term secure availability of the raw material basis is one consideration. Beyond that,
the further development of these biopolymer materials will mainly emphasize additional
technological aspects, such as heat resistance, smell, brittle fracture behavior, coloration, UV
stabilization, and long-term reliability. Other hot topics will be the development, test and
use of appropriate biopolymer additives [ll, 341, as well as the optimization of biopolymer
manufacturing and processing properties (Fig. 2.4).
Research is currently focused on the growing variety of bio-based raw materials and the optimization of use properties or to retain known properties of conventional plastics. Currently,
work is being intensified on so-called "drop-in solutions" by large chemical companies, such
as Bayer, BASF, Dow Chemical, Baskem (Brazil), DSM, and Solvay. Here, the conventional
methods of synthesizing petrochemical plastics are being maintained using biogenic raw
materials. For example, polyvalent biogenic alcohols or bio-based carboxylic acids are being

22

State of Knowledge

Usage of biopolymers
Development

1st Generation
R&D for approx. 20 years
No commercial usage
, Poor material properties
, Unfavourable political and
commercial conditions
, Not enough ecological
pressure in politics and
industry

2nd Generation

3rd Generation

Packaging applications

Technical applications

, short-lived uses
, Compostable / certified

, e.g., automotive applications

, .g., textile- and fiber
industry

Agriculture applications
, short-lived uses partly
without disposal
requirement
, ithout disposal
, Certifications are unnecessary

Modifications necessary
, Copolymers and blending
, se of additives / stabilizers
, se of fillers
, se of reinforcements

Medical applications

Figure 2.4 Third generation biopolymers- from degradability to durability

used to produce polyethylene (bio-PE), polyamide (bio-PA), polyurethane (bio-PUR), and

various polyesters.

2.3

Biological Degradability and Compostability

Biodegradableplastics consist of natural (renewable)resources or syntheticbuilding blocks (fossil raw materials) and are accessible for biological reactions. That means they decompose under
exposureto microorganisms and/or enzymes [15].Generally speaking,biodegradation processes
in plastics initially lead to changes in various properties, such as mechanical characteristics,optical appearance (surface structure, coloring, etc.), odors, or increased permeability (Fig. 2.5).
Furthermore, we can distinguish materials dissociation as either induced primary degradation (macromolecule splitting) and final degradation of decomposition products to water,
carbon dioxide, methane, and biomass [35-401 (see Fig. 2.6).

Figure 2.5 Macroscopic degradation of a biopolymer film (Source: BASF SE)

2.3

Biological Degradability and Compostability

23

Figure 2.6 Primary and final degradation

In the course of total biological degradation, microorganisms in fact require extracellular

enzymes to digest plastics and/or their molecular decomposition products. These enzymes
essentially use oxidation and hydrolytic processes to break the material down into even
smaller components, which can then be absorbed by the cell [41-431 (see Fig. 2.7). However,
the enzymes are too voluminous to penetrate the degrading material efficiently. Therefore,
No direct transport
into the cell

Microbial cell

Cellulose
H
HO

H
OH
H

CH2OH

H
CH2OH

HO

H
O

O
H
OH
H

Extracellular enzyme

Endoglucanase

Exoglucanase

Glucosidase
CH2 OH
HO

O
OH

HO
OH

Glucose

Figure 2.7 Cellulose degradation due to cellulase enzyme complexes

24

State of Knowledge

Figure 2.8 Examples of heteroatoms in the macromoleculesof biologically degradable polymers

this process can function only as surface erosion, or as a diffusion-controlled sequence in

liquid carrier media, especially water.
Biodegradation can take place under a wide variety of ambient conditions (ground, water,
seawater, compost, the human body, etc.). Biodegradability is based mostly on the presence
of so-called heteroatoms (not carbon) in the main chains of the macromolecules (cf. Fig.
2.8). These heteroatoms provide a point of access for microorganisms to split the chains, thus
inducing a primary depolymerization and degradation process. The further final degradation
sequence is due mostly to intracellular metabolizing reactions by the corresponding microorganisms [9, 351 (Fig. 2.8). Whether decomposition products can be metabolized determines
whether the process involved causes macroscopic disintegration of a part or a material (primary
degradation) or in fact complete, final degradation. If the final degradation of decomposition
products is not assured, i. e., in the case of primary degradation, decomposition products may
accumulate in compost or ground water.
In general, degradability increases fundamentally as the ratio of heteroatoms to carbon
increases, in particular in the main chain (Fig. 2.9). Even total biodegradation of a mate-

Figure 2.9 Biodegradability as a function of the carbonlheteroatom ratio in the main chain

2.3

Biological Degradability and Compostability

25

Figure 2.10 Scanning electron microscopic exposure of a polymer surface attacked by microorganisms

rial still does not automatically mean that the material or parts produced from it are also
compostable. A material is considered biodegradable if all its organic components generally
and regardless of any time factor are subject to primary and final degradation by biological
activity, see Fig. 2.10 136,441.
A material or materials mix and parts produced from it is considered compostable, when,
under defined conditions in a composting system, it is entirely transformed into COz, HzO,
CHI, and biomass within a specified length of time, i. e., mostly during a composting cycle
ranging from a few weeks to months [45,46]. For example, a tree trunk is biodegradable, but
not compostable.
In principle, biodegradability and compostability of biopolymers and/or products made from
them increase with certain factors due to the resulting simplified access for microorganisms
to the molecules, thus enhancing metabolizability (see Table 2.1).
The standards for certification of compostable materials are discussed in more detail in
Sections 3.1 and 3.2.
Table 2.1 Degradability as a Function of Various Microstructural Parameters (t = Increase,
= Reduction)

Microstructural parameters

Degradability

Intermolecular interaction, crystallinity

Number of unsaturated compounds

Unbranched, flexible molecular structures

Aromatic portion

Molecular weight

Polarity/swelling

Specific surface

26

State of Knowledge

During molecular degradation, primary degradation is initiated not only by biologically

induced decomposition reactions, but also by other degradation mechanisms. One of these
mechanisms is macromolecule scission due to radiation. The most important natural radiation in this respect is the UV content in sunlight. The exposure to sunlight can result in direct
polymer chain scission, particularly in polymers with chromophore groups in their molecular
structure, e. g., aromatic polyesters or polyamides (photodegradable polymers) [4,38,40].
Catalyst residue, contamination, peroxides, as well as other oxygenic components can also
absorb sunlight and initiate degradation. Indirect chain scission processes use host molecules,
such as aldehydes or conjugated double bond systems; they are excited by radiation and in
a second step, the energy required to split the bond is transferred to the actual polymer
molecule.
Besides this pure photodegradation, sunlight in combination with oxygen also causes photooxidative degradation. Heat or the effect of light can initiate an 0x0-degradation sequence
by radical formation. Next, alkyl radicals can form and once they react with oxygen, lightsensitive hydroperoxides can form as an intermediate step of photo-oxidative degradation.
Continued exposure to light and elevated temperatures together with the previously formed
hydroperoxides cause continued radical formation (alkoxy, peroxide, and alkyl radicals),
until the polymer chains ultimately degrade. Reaction products such as carboxyl acids or
alcohols are subject to further final degradation.
Current research is concentrating on the 0x0-degradability of polyolefins, especially
PE, by incorporating special metal ions to initiate a radical oxidation mechanism. However, this 0x0-degradation method is very controversial. According to most experts, total
microbiological final degradation generally has not been reached in oligomer decomposition products until they are reduced to less than 20 to 25 C atoms [4]. The decomposition
products of polymer 0x0-degradation are usually much larger. In order to obtain smaller,
completely degradable oligomers for total degradation, high doping levels are required,
which in turn cause a considerable and generally unacceptable decrease in materials
properties.
Another method of initiating primary degradation is a sequence of water dissolution followed
or accompanied by hydrolysis (water soluble polymers) (Fig. 2.11).
These different reaction mechanisms have in common that they can lead to macroscopic
primary degradation, without ensuring final degradation of the products of decomposition
Degradable
polymers
Photo-degradable
polymers
Petrochemical
raw materials

Renewable
resources

Bio-degradable
polymers
Petrochemical
raw materials

Renewable
resources

Figure 2.1 1 Degradation mechanisms in degradable polymers [47]

Watersoluble
polymers
Petrochemical
raw materials

Renewable
resources

2.5

Resource and Land Requirements for Manufacturing Biopolymers

27

(cf. Fig. 2.6). Therefore, total biological degradability or compostability of materials cannot
automatically be presumed, even when there is macroscopic disintegration or macrobiological damage and a reduction and/or loss of mechanical properties, surface change, or odor
development.

2.5

Resource and Land Requirements for Manufacturing

Biopolymers

Natural materials produced by agriculture or forestry can be utilized both as food or feedstock
as so-called renewable resources for engineering purposes (Fig. 2.12). Faced with limited
arable land areas and high demands for food stocks, especially in the developing world, biobased polymers are considered with the same significance as food and energy when weighing
in on the use of land and/or the natural resources produced on it (common buzz phrases are
"empty plates or empty tanks" or "fuel, food or feed") (Fig. 2.13).
Natural materials

Food stuff

Food and
Beverage

Herbs and
Spices

Renewable resources

Medicinal
plants

Chemical/
industrial
utilization

Material/
technical
utilization

Energetical
utilization
(biomass)

Biotechnol.
utilization
(biomass)

Figure 2.1 2 Use of natural products as food or feedstock or as renewable resources for engineering
purposes

However, the extent to which this takes place is not justified. Compared to the area under
cultivation for food or for use as renewable energy sources, bio-based polymers require
significantly less land area, while their use efficiency and substitution potential is clearly

Figure 2.13 Competition for the use of renewable resources

28

State of Knowledge

higher. This means that, for example, an area at least 3.6 times the total land area (not land
for cultivation) of Germany would be theoretically required to substitute Germany's crude
oil demands completely by vegetable oil. On the other hand, only 25% of Germany's entire
land area would have to be utilized to theoretically substitute its entire production of plastics
(20 mio t/a), Fig. 2.14.
To fulfill Germany's demand for electric power by incinerating biomass would require approx.
1.5 times the land area of Germany. Approximately 0.8 of Germany's land area would have
to be utilized to substitute the German demand for diesel fuel and gasoline with biodiesel
and bioethanol. The precise figures for energy and raw materials demands on which these
estimates are based are presented in Table 2.2.
The data on energy yields are based on an average of 800 t/kmz biomass production with a
heat value of 15 MJ/kg and 30% efficiency when burned to generate power.
The average biopolymer yield of 250 t/kmz.ais based on the average yield of the particular raw
material (e. g., starch, sugar) and on the particular raw materials demand for the production
of the various biopolymers and/or the final bio-based materials components. Figures 2.17 to
2.20 provide more detailed individual raw materials yields for different renewable resources
and the corresponding raw materials demands for manufacturing the various biopolymers,
as well as the resulting theoretical biopolymer yields per km2and year.
A more realistic scenario (Fig. 2.15) is a substitution of 20% of German oil, power, fuel, and
plastics demands, in particular when comparing the land area required then to the currently
available land used for agriculture in Germany (instead of the entire land area).
That means that approx. 16,000kmzwould be required to substitute 20% of the polymers in
German plastics production with biopolymers, i. e., 4 million of 20 million tons annually
(assuming an average biopolymer yield of 250 t/kmz.a). This amounts to approx. 9% of the
land area in cultivation in Germany (170,000 kmz).
Thus, to ensure the current worldwide total production of biopolymers (approx. 0.8 million
tons annually), approx. 0.01-0.02% of the world's cultivated land area (Fig. 2.16) would be
needed.

Figure 2.1 4 Land requirementsfor substituting each energy source and/or material with renewable
resources relative to total land mass of Germany

2.5

Resource and Land Requirements for Manufacturing Biopolymers

29

Table 2.2 Land Use, Land Productivity,and Use Data Worldwide, USA, EU 25, and Germany (Status:
200712008)

World

USA

EU 25

Germany

Total land area

[106 km2]

150

9.83

4.35

0.36

Land under cultivation

[106 km2]

15.5

1.96

1.80

0.17

35

4.50

1.95

0.11

Oil consumption
[106 t/a]

4,100

1030

730

130

Current consumption
[109 kWh/a]

16,500

3,750

2,850

540

Passenger car fuel consumption

[106 t/a]

1,500

300

250

50

Plastics generation
[106 t/a]

260

70

65

20

Average vegetable oil yield

[t/km2 a]

350

170

100

100

Average biopolymer yield

[t/km2 a]

250

250

250

250

Average bio-diesel yield

[Liter/km2 a]

150,000

200,000

150,000

150,000

Average bio-ethanol yield

[Liter/km2 a]

400,000

400,000

250,000

250,000

1,500

1,200

1,130

1,130

Forestry
[106 km2]

Average biomass-based energy yield

[kWh/km2 a]

Even with an increased market share, using renewable resources to manufacture biopolymers
requires significantlyless land area than the comparableproduction of corresponding quantities
of biogenic energy. With this low demand on land use for manufacturing bio-based biopolymers
in mind, there already are other industrial sectors in which significantly higher amounts of
renewable resources are currently used without being subject to extensive ethical discussions.
For instance, the paper industry annually uses approx. 5 million tons of food-quality starch
to produce paper. By contrast, currently approx. 350,000 tons of starch are used annually to
manufacture biopolymers, i. e., only approx. 7% of the starch used by the paper industry.
To evaluate the land demands for biopolymers, we will first consider the annual yields of the
various renewable resources more closely. A large range ofvariation in yields is the result ofthe

30

State of Knowledge

Figure 2.1 5 Land requirements relative to the cultivated land area of Germany in order to substitute
20% of each energy source and/or material with biobased energy sources and/or biobased materials

Figure 2.16 Worldwide use of several renewable resources for engineering purposes

different climatic and geographical conditions for cultivation, as well as of different degrees of
extensiveness of cultivation. Due to the intensive European cultivation, the maximum yields
among renewable resources cultivated in Europe are reflected in the peak European yields,
whereas the lower values mostly represent the averages from worldwide cultivation.
In Fig. 2.17, first the yields of the individual renewable resources are represented in order to
determine absolute yields.
These are only the absolute yields of the individual renewable resources regardless of their
differences in added value or different requirements for cultivating and obtaininglisolating a
particular renewable resource. In addition, to facilitate a comparison, this figure was subdivided into groups for sugar, starch, vegetable oil, and cellulosic (fibrous)raw materials. It can be

Resource and Land Requirements for Manufacturing Biopolymers

31

2,500

2,000

1,500

1,000

500

Sugar

Starch

Vegetable oil

Coon

Flax

Hemp

Wood pulp

Wheat straw

Soy oil

Rapeseed oil

Sunower oil

Caster oil

Coconut oil

Jatropha oil

Palm oil

Rice starch

Wheat starch

Corn starch

Potato starch

Sugar (beet)

0
Sugar (cane)

Raw material yields per km [t /(km*a)]

2.5

Cellulose(bers)

Figure 2.17 Absolute annual area yields of various renewable resources

seen that sugar plants supply top yields among renewable resources. Starch plants also supply
relatively high resource yields, whereas the yields of corresponding renewable resources from
plants supplying oil and cellulose are fundamentally lower by comparison. When it comes to
oil, only palm oil and jatropha oil supply yields similar to that of starch cultivation.
In order to obtain the annual amount of biopolymers that can be produced per area (biopolymer yield per acre), Fig. 2.18 provides the materials percentage based on the individual
renewable resources. Blends in particular exhibit a wide range of bio-based material contents
because they often also contain petrochemical blend components.
In addition, for the bio-based materials percentages presented here it is important to know
the efficiency of converting the particular resource, i. e., the particular initial amount of each
renewable resource required for the bio-based materials components. Figure 2.19 shows the
representative ratio of renewable resource input to total materials yield based on the particular bio-based materials percentage and the corresponding raw materials charge required
for each. For ethanol as an intermediate step, for example, a yield of approximately 0.5 tons
was assumed per ton of sugar. It is important to note that almost no biopolymer is 100% biobased. Sometimes the materials percentage based on renewable resources is less than 30 wt.%,
so that 70 wt.% of the material does not require land area, because it is not based on renewable
resources. Thus, as a general rule, the lower the bio-based content in a material is, the higher
is the resulting absolute amount of material relative to the area cultivated. This can be seen by
comparing Figs. 2.18 and 2.19, which exhibit fundamentally reversed proportionalities. Thus
it is not sufficient simply to state the biopolymer yield per unit area without considering the
percentage of bio-based material in any given materiallblend.
To determine the biopolymer materials yields presented in Fig. 2.19 in relationship to the
input of renewable resources, the following assumptions were made:

State of Knowledge

Percentage of raw material based on

renewable resources in biopolymer

32

100%
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%

[Output: t biopolymer or t bioethanol /

Input: t bio-based raw material]

Figure 2.1 8 Percentages of materials weight in various biopolymers based on renewable resources

6
5
4
3
2
1
0

Figure 2.19 Biopolymer yield vs. input of renewable resources

1: Cellulose Acetate (CA): 40-50 wt.% cellulose-based materials

Even in partially biodegradable cellulose acetate, at least approx. % of the hydroxyl groups in
the glucose unit are replaced by acetate groups (cf. Section 4.2.3.3). That means the degree of
substitution is generallyhigher than 2.0; in addition, up to 30 wt.% non bio-based plasticizers
are used in cellulose derivatives. Therefore, it was assumed that the percentage of cellulose
based materials in cellulose acetate ranges from 40 to 50 wt.%. That also means that up to
60 wt.% of the material is not based on cellulose, but on acetic acid anhydride or acetic acid
(produced on a large technological scale mostly by catalytic conversion of petrochemical

2.5

Resource and Land Requirements for Manufacturing Biopolymers

33

methanol with carbon monoxide under pressure) and additional petrochemical plasticizers.
Assuming a minimum substitution degree of 2, the percentage of acetate alone is already
approx. 30% and plasticizers make for approx. 20% by weight.
2: Cellulose Regenerate: 90-99 wt. % cellulose-based materials

In the biopolymer field, cellulose regenerates are used mostly as coatings (e.g., as barrier
layer, sealing layer) with film materials. For the matrix, which makes up most of the weight, a
cellulose content of nearly 100% can be assumed. Max. 10 wt.% can be assumed for the coating
and possibly remaining processing agents.
3: Thermoplastic Starch (TPS): 70-80 wt. % starch-based materials

In order to optimize the processing and use properties of thermoplastic starch polymers,
native starch has to be modified, and/or plasticizers such as glycerine or sorbitol have to be
added. On average 70-80 wt.% of material can be assumed to be directly starch-based. At the
same time, a 100% conversion to biopolymeric material was assumed for unmodified starch.
Analogous to cellulose acetate, a high degree of substitution was assumed for starch acetate,
leading to a starch requirement of only 600 kg per ton of starch components. A petrochemical
raw materials base was presumed for the remaining additives and plasticizers.
4: Starch Blends: 30-85 wt.% starch-based materials

In order to optimize the processing and use properties of thermoplastic starch polymers,
native starch - as previously stated - has to be modified or blended with other biopolymers.
The second component usually represents the continuous phase in the blend. Thus, for starch
blends, 30-85 wt.% was assumed to originate from starch. This calculation is based on the
values for thermoplastic starch in Case 3. For the remaining 15-70 wt.% of the starch blends
a petrochemical-based material is assumed.
5: Polylactic Acid (PLA): 90-97 wt. % PLA-based materials

For PLA polymers based on lactic acid it was assumed that only 3-10 wt.% of functional
additives (nucleation aids, pigment batches, stabilizers, etc.) was added to the PLA. Corn
starch was the raw material presumed for PLA. It was also assumed that approx. 0.7 ton of
PLA are obtained from 1ton of corn starch.
6: PLA Blends: 30-65 wt.% PLA-based materials

Because these rather ductile PLA blends are typically used in films, they consist of a maximum of 65 and a minimum of 30 wt.% PLA-based materials. The PLA values from Case 5
were assumed for PLA blend components. The second blend component was generally a
bio-polyester. The values used in Case 9 were also used for the biopolyester blend portion. In
addition, a petrochemical based additive content of 5 wt.% was assumed for PLA blends; they
are used, e. g., to improve interaction between both materials phases or as processing aids.
7: Polyhydroxyalkanoates (PHAs): 90-98 wt.% PHA-based materials

For polyhydroxyalkanoates (PHAs) produced by fermentation, on average a 90-98% biobased materials content was assumed due to their low additive content. To manufacture 1ton
of PHA, 4 to 5 tons of sugar are required.
8: Bioethanol
A 100% sugar base was assumed for the production of bioethanol as an intermediate step in
particular for bio-polyethylene and various bio-polyesters. In addition, it can be presumed
that between approx. 1.7 ton and 2.7 t of sugar are required for 1t of bioethanol.

34

State of Knowledge

9: Bio-Polyester:30-45 wt. % bioalcohol; remaining materials basis: petrochemical

To determine the conversion efficiency for bio-polyesters, an average bio-based alcohol
content of 30-45% was assumed. That means that 55-70% wt.% of so-called bio-polyester
materials is not based on renewable resources. To determine the bioalcohol content, the
material requirements for bioethanol detailed in Case 8 were used.

[t biopolymers / (km*a)]

10: Bio-Polyethylene (bio-PE):95-98 wt. % bioalcohol based materials

As with conventional PE, an additive content of 2-5 wt.% was assumed, so that bio-ethylenes
are 95-98 wt.% bioethanol-based materials. In addition, it was assumed that 2.3-2.5 t of ethanol were required to produce 1t of polyethylene. Again, the data from Case 8 were applied
for the bioethanol content.
Annual biopolymer yields relative to unit area were subsequently determined. To do so, the
individual theoretically achievable annual yield per unit area of the various biopolymers,
shown in Fig. 2.20, was calculated from the specific bio-based materials percentages of biopolymers (cf. Fig. 2.18), the specific amount of renewable resource input required (cf. Fig. 2.19),
and the corresponding annual yield of renewable resources per unit area (cf. Fig. 2.17).
Not only do the yields of the various renewable resources vary widely, but it is also possible
to utilize different biogenic raw materials (e.g., starch or sugar) to manufacture the same
biopolymer, so that bio-based material contents also vary widely. The final result is a wide
range of variation in the theoretically calculated biopolymer yields per unit area.
Economic factors motivate biopolymer manufacturers to strive for maximum utilization of
material and the highest possible yields per unit area; therefore, comparing the higher values
in each case provides a better picture of the actual trends in biopolymer yield per unit area.

3,500

 









 



 

 
 

3,000
2,500
2,000
1,500
1,000
500
0

Figure 2.20 Minimum and maximum possible biopolymer yields per km2and year. Note: the
biopolymers are not entirely 100% bio-based. In some cases, the percentage of bio-based material is
less than 30wt.%

2.6

Sustainability and Entropic Efficiency of Biopolymers

35

Raw material supply security

Bio-based polymeric materials
 

"+$ &$ .($*# 

+-

,


~ 2100 cars / km*a

)/ 

)&
$+
" + %
10 years service life
*.$+("  ,$+( * # 

per car
+ ,$
% ! , 

Biofuels
 



+-
 
*

)/

~ 20 cars / km*a
,' *

+-
 
*



.$ +
)/

fuel consumpon
(#($$*

+-
 
*

)/
  
*


)
# 
)


Figure 2.21 Comparison of supply security for biobased materials and fuels

For example, bio-PE exhibits the lowest area efficiency, despite the high sugar yield relative
to the producible quantity of biopolymer, because of the high amount of sugar required to
produce bioethanol and the high amount of ethanol required for polymerizing polyethylene.
As a contrasting example, PLA (plus additives) with a high percentage of bio-based material
is characterized by high area efficiency due to its better rate of conversion during fermentation. The yields per unit area of PHAs are low, due in part to the high input of raw materials
for fermentation. As with bio-PE or cellulose regenerates, the relatively low area efficiency
of PHAs can also be due to their high percentage of bio-based material and/or the lack of a
materials component not based on land area and/or bio raw materials.
Conversely, the high percentage of materials components not dependent on biogenic raw
materials results in seemingly high area efficiencies for bio-polyesters, starch blends, PLA
blends, and cellulose acetate. However, this perceived efficiency is the result of adding significant amounts of area-independent petrochemical material components.
What is essential, however, is the fact that biopolymers exhibit higher area efficiency compared to biofuels in addition to their significantly lower absolute quantities, which will help
them gaining visible market shares in the plastics sector

2.6

Sustainability and Entropic Efficiency of Biopolymers

The concept of sustainability may be used increasingly in nearly all branches of science, business, ethics, politics, and industry, but for the sciences, it is vaguely defined and interpreted
in various ways. However, all definitions of sustainability have one thing in common: a
formulation for maintaining a system and/or particular characteristics of a system for the
good of future generations. The system may be very different in type and size, such as the

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State of Knowledge

production capacity of a regional or national social system, or the maintenance of a global

ecological system.
The roots of the sustainability concept reach back into the lgthcentury. Faced with the threat
of wood shortages and in view of the expected demands on wood supply by beginning industrialization, sustainability became established as a fundamental principle of forestry all over
Europe. For some 250 years, sustainability has been a main principle of action in forestry,
i. e., the same quantity of wood is harvested that renews itself, or the same quantity of wood
is replanted as is harvested.
Today, we often differentiate sustainable action according to the system under consideration,
i.e., we distinguish between ecological, economic, and social sustainability Within this
framework the environment, human society, and economic systems are treated as superordinate systems, Fig. 2.22.

Greenhouse effect, resources, pollutant, ozone depletion

Soil fertility

Eco-efficiency

Water

Long-term
investment

Innovation

Environment

Health

Safety

Scope of action

Recovery cost

Prosperity

Economy

Society

Education

Information

Intergenerational contract

Taxes, fees, subsidies, solidarity, jobs

Figure 2.22 Social, economic and environmental sustainability (source: Carbotech AG, modified)

Figure 2.23 Terminology in the context of environmental sustainability

2.6

Sustainability and Entropic Efficiency of Biopolymers

37

By ecological sustainability we generally mean that raw materialdenergy sources, and

the conversion processes/emissions they entail, may only be used in such a way that selfmaintenance, renewability, and environmental stability of the system remain intact together
with its essential characteristics.
All systems naturally present on Earth are characterized by clear environmental sustainability.
For example, in contrast to the quantity of waste generated by humans, nature creates only
as much biomass as can be degraded in the same time. As biomass degrades in nature, the
amount of CO, generated equals the amount metabolized for creating new biomass. The same
equilibrium exists for the other elements involved in creating and degrading biomass.
However, the disproportional anthropogenic removal of resources, such as wood (rain forest
destruction) or water (drying up the Aral Sea), or the addition of substances, waste materials, and emissions (e. g., COz, CFC's and other greenhouse gases, ocean acidification, acid
rain, eutrophication) can transform the Earth's ecosystems into a condition that cannot be
considered naturally renewable on a human time scale. The law of conservation of mass is
still valid, but the exhausted resources (e. g., crude oil) will no longer be regenerated at the
same rate, nor will the conversion products made from it (e.g., plastics) or the generated
waste decompose at the same rate and become available again as raw materials resources.
This is especially the case for the use of crude oil as an energy source, as well as for the pace
of crude oil utilization. We generate many times the CO, that is sequestered in biomass and
re-converted into crude oil during the same time span. In other words, each year we use up
a quantity of crude oil that was created over millions of years, and whose recreation will take
several million years. In order to sequestrate the anthropogenic CO, generated by the use/
burning of petrochemical raw materials in forests, a wooded area roughly twice the size of
the current world's forests would be required.
That means that we are limiting the options and the development of future generations by
our current use of limited abiotic resources, such as crude oil, natural gas, uranium, metal
ores, or water, air, and land. For example, in order to provide the approx. six billion people
on Earth with the same living standards enjoyed by the average citizen of an industrialized
country, three Earths would be needed to ensure the quantity of raw materials, energy, and
waste disposal required. This behavior is not sustainable.
However, this statement is a generalization and thus, in this form, not yet suitable for a
quantifiable evaluation of a process or product for its sustainability. Therefore, eco-balancing
or so-called Life Cycle Analysis (LCA) is used for evaluating the sustainability of a material,
product, or process. This is generally done by comparing the product to be evaluated with
a competitive product, or by directly comparing different processes, whose usefulness are
equated for the sake of simplicity. Evaluation is then based on the measuring of emissions
generated by each, as well as on the quantitative evaluation and weighting of various environmental effects (a precise description of LCA methodology is presented in Section 7.1). This
evaluation considers only the product or product related quantities emitted and not their
reversibility or the time and effort required to reverse the process investigated and/or the
emissions it necessarily entails. LCA thus gives only limited consideration to the irreversibility of a process as an important parameter. The redistribution of matter over the entire life of
a product including its disposal is only marginally considered in the evaluation. For instance,
COz emissions from biological degradation of organic substances are not ecologically bad in
itself. The problem is not the existing or generated quantity of COz, but the irreversibility of

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State o f Knowledge

the increase in the amount of C 0 2due to the emission of irreversible C02.Nature is capable
of reversing the process with the help of solar energy, that is, of "arresting" C 0 2 released
during biomass degradation and incorporating it back into organic biomass. By contrast,
renewed incorporation of carbon dioxide released by burning crude oil cannot, on a time
scale relevant to humanity, be considered part of a reversible process, because it would take
millions of years to form crude oil from biomass. The effects of a bio-based or petro-based
CO, molecule, however, are the same, regardless of origin.
Another problem for LCA is the assumption of equal usefulness for comparative evaluation.
However, when different processes/products are to be compared, the solution that generates
maximum usefulness while doing the least ecological damage is the most sustainable one.
That is why the concept of entropy, better yet entropic efficiency, is the far better tool for
evaluating the ecological sustainability of a material, product, or process from an economic
point of view. Instead of assessing the ecological impact from production, use, or disposal of
a process or product, it considers the effort and expense of returning the system or product
components to their original state relative to the usefulness of the process or product.
The energetic and material use of fossil raw materials inevitably leads to a redistribution of
matter and to a devaluation of our planet. According to the first principle of thermodynamics,
the law of conservation of matter and energy, neither energy nor matter can be created or
destroyed. However, the transformation of one energy form into another, or the use of matter
always involves losses and leads to a less useful form of energy (anergy) or matter.
This enables us to explain why the transformation of fossil carbon into COz is, on a human
time scale, a one-way street. It also explains how we can complain about the temperature
increase due to the greenhouse effect on the one hand, and worry about the security of our
future energy supply on the other. The problem here is that the heat energy increasing in the
atmosphere cannot really be put to energetic use for humanity, Fig. 2.24.
This is the content of the second principle of thermodynamics, the law of entropy. Human
activity tends to devaluate energy and matter. Useful forms are converted either into less
useful ones or into less transformable energy forms (e. g., kinetic energy into heat) and forms
that are less efficient (e. g., crude oil into CO,). Entropy, simply stated, is a measure for the
Release of
CO2

CO2

Heat

Irreversible
entropy
increase

Greenhouse
effect

Utilization/
Combustion of fossil
raw materials

Figure 2.24 The use of fossil resources causes the release of heat and C02, i.e., to an irreversible increase
in entropy

2.6

Sustainability and Entropic Efficiency of Biopolymers

39

irreversibility of this transformation process. In the case of energy, the entropy generated by
the transformation process corresponds to the loss of regainable energy/work (exergy). That
means that only idealized, totally reversible processes do not generate entropy. Thus in reality,
entropy is generated in every anthropogenic process of transformation, Fig. 2.25.
The same argument holds for the redistribution of matter. The redistribution of matter, such as
CO, emissions from combustion, or the creation and distribution of waste, leads to increased
disorder and/or entropy on Earth. In order to restore the "old condition of order'', energy
has to be applied in another place. That means that, in order to reduce entropy by increasing
the state of order in one place on Earth, entropy is generated in another place. However, due
to the fact that the efficiency of real transformation processes is always less than 1, the total
sum invariably includes an increase in entropy. Moreover, since we cannot compensate for
entropy once it is formed, our sustainable action must attempt to minimize the generation
of new entropy, i. e., reduce the percentage and amount of irreversible transformation processes. Entropic efficiency can be represented by the ratio of product/process usefulness to its
generation of entropy over the entire product life including its disposal/recycling. Maximum
sustainability of a product or process means minimal generation of entropy over the entire
life cycle together with maximum usefulness (Fig. 2.26).
The production of renewable resources as polymer raw materials via photosynthetic processes
is a procedure that actually leads to an increased state of order and thus to a reduction of
entropy on Earth. Plants arrest finely distributed C 0 2and sequester the carbon and hydrogen
in form of biomass with the help of solar energy. Even though solar energy is considered
regenerative energy in human dimensions, solar heat generation is not a reversible process.
From a scientific point of view, this is also an irreversible process in which heat generation leads to a parallel production of entropy on the Sun. This means that this generation of
entropy on the Sun leads to C 0 2sequestration, i. e., an increased state of order or reduction of
entropy on Earth by photosynthetic reaction. Fundamentally, it can be said that, when we use
the sun or other regenerative energy forms, we utilize primary sources of energy or energies
without any entropy being produced on Earth by their creation.
By contrast, transforming CO, to reclaim carbon with the help of technical processes requires
the use of energy whose generation involves the production of entropy somewhere else. If
regenerative energy is utilized for the transformation of CO,, this is the same as natural
photosynthesis in which CO, is sequestered in biomass, i. e., in organic polymers, also using
Entropy

Processes
A

Figure 2.25 Anthropogenic transformation processes cause continuous and irreversible increases in
entropy

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State of Knowledge

Primary raw materials

(plants, iron ore, crude oil)
Energy / energy source
(hydropower, oil)

Information

Raw material
(iron, ethylene,
cellulose, starch)

Incin
Pyrolyesration
is
A

Recy

cling

C O2

fill

Land

E Waste, scrap

Material grade M

(steel, plastic,ceramic)

F Failure
Design
(buildings, machines, parts,
packaging, products)

D
U

Utilization

Figure 2.26 Entropy efficiency over an entire product life cycle for assessing sustainability

regenerative solar energy. Moreover, the technological processes that can be implemented to
reclaim carbon are extremely inefficient, even when regenerative energy is used.
For transformation processes, it is fundamental that the absolute quantity of the energy
required is entirely decoupled from the question whether the energy utilized was or is of
regenerative origin. A transformation process does not automatically become better when
regenerative energy sources are used. After all, once this energy is available, it can also be
used for any other process. Specifically, biopolymers do not become more sustainable if
regenerative energy was utilized to polymerize them. The same regenerative energy can also
be utilized to polymerize a conventional polyethylene. In this case, a more sustainable energy
source is only being used in the process of polymerizing a polymer.
At the end biopolymers exhibit in principle high entropic efficiency not only with regard to
raw materials, but also regarding their disposal.
Raw materials:
no redistributionlmixture of petrochemical raw materials
lower energy use for manufacturing raw materials thanks to prior natural synthesizing
reclaiming of carbon
regenerative process for raw material synthesis, i. e., bio-based raw materials will be available in the long term
Disposal:
biopolymers can be disposed of by natural processes
composting requires little additional energy
biopolymers are a suitable co-substrate in biogas plants for conversion into the energy
source methane
incineration provides additional energetic use and is CO, neutral

2.7

The Proprietary Situation of Biopolymers

41

The C02-neutraluse of bio-based materials and their additional use for incineration or biogas
generation results in a cascading use, minimizing COz and at very low cost.
Another way to notably increase entropic efficiency when biopolymers are incinerated to
generate electricity or added to any biomass used to generate electricity is to significantly
increase thermal use parallel to COzneutral emissions. At the current average total efficiency
of approx. 30%,only about 113ofthe biomass incinerated is directly transformed into thermal
energy when biomass is used to generate electricity in coupled heat-power plants or in biogas
plants without heat-power coupling. That means that approx. 213 ofthe biomass-based CO, is
produced without technical utilization and releases additional negative greenhouse energy.
It is too simple and often even false to automatically use the label of sustainable materials
when mentioning biopolymers that are based entirely or partially on renewable resources
or capable of biological degradation. In order to assess sustainability, the irreversible cost
of energy and material has to be considered over the entire life span. This involves not only
the production of raw material (e. g., fertilizer, herbicide), raw materials production, isolation and cleaning (e.g., water and energy to produce starch, pulping), transport, and finally
polymerization. From this point of view, even composting is not necessarily sustaining, if too
much energy is required for collecting, sorting, and transporting compostable biopolymers
1481.
Conversely,the use of conventional petrochemical polymers is not necessarilynon-sustaining.
Considering the total life span, their benefits exceed the use of petrochemical raw materials1
plastics or the technological expense of disposing of these plastics. This can be illustrated for
packaging by the following example:
If, for example, the use of known plastics were eliminated in the packaging field, substituting
them would mean multiplying weight by using alternative packaging materials such as glass or
metal. In view of these much heavier packaging materials with the same benefits, the energy cost
of transporting or using plastics packaging is often much lower due to their lower density.
If we pursue this scenario a step further, then the total elimination of packaging materials,
especially plastics packaging, would result in a total loss of shelf life, storability and transportability, i. e., the capability to distribute food. Instead, food would have to be transported
directly to the consumer immediately following harvesting andlor production for immediate consumption. Although this would decrease entropy, the food would lose much of its
benefit. Moreover, additional energy would be required to distribute food for immediate food
consumption. This alternative would thus ultimately increase entropy generation, while both
benefits and entropy efficiency would suffer.

2.7

The Proprietary Situation of Biopolymers

Increasing interest in the field of biopolymers in recent years is reflected in the number of
patent applications in the field. The number of applications has increased with double-digit
growth rates, Fig. 2.28. In the field of thermoplastic starch polymers alone, approx. 1,000
patents have already been applied for.

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State of Knowledge

Increase in patent activity regarding biopolymers

1,200
1,000
800
600
400

2000

1997

1994

1991

1980

200

Number

Figure 2.27 Worldwide patent applications in the field of biopolymers [491

Figure 2.28 Areas of applications for the most important biopolymers covered by European patents

In Europe alone, there are well over 500 patent specifications in the biopolymers field. Both
in the US and the rest of the world (especiallyAsia), there are approx. twice the number of
patent specifications each, i. e., we can presume the existence of far more than 2,500 patent
specifications.
The patent content reflects the areas of interest on which the corresponding research activity
is focused. The push towards the development ofbiopolymers originated in Europe. However,
compared to conventional polymer manufacturers, there are relatively few manufacturers of

2.7

The Proprietary Situation o f Biopolymers

43

biopolymers in Europe, but at the same time there is a large number of plastics processors.
Together with an increasing environmental awareness in Europe and the fact that Europe
has few oil reserves of its own, this was a trigger for a plethora of patents in this field. A
closer evaluation of the patents granted shows, for example, that the European biopolymer
patents focus less on new monomers or materials development, but rather on processing
and application (e. g., for packaging), as well as on the manufacture of composites and the
production of biopolymer blends.
A closer look at the applications as well as at the most important biopolymer properties targeted by the various patents reveals that the focus in Europe, and especially in Germany, is on
bio-degradability and product compostability. The second generation biopolymers described
earlier was developed in Europe, typically for applications in the field of compostable packaging. Therefore, the developments in Europe in the last 10 years have focused mainly on the
processibility of biopolymer materials for packaging material and packaging aids, on properties specific to packaging, as well as on disposal via biodegradation processes, Fig. 2.29.
In Asia, by contrast, biopolymer development began some 10 years later. However, the development of third generation bio-based and durable engineering polymers and their use for
long-term engineering applications outside the packaging field began simultaneously several
years ago. Conversely in Europe, the use of bio-based materials for engineering applications
gained increasing interest in research and materials development only in the last couple of
years.

%
%

%
%

%
Figure 2.29 Representative distribution of preferred biopolymers properties targeted by European
patents