The Reality Behind Biodegradable Plastic Packaging Material

The Science of Biodegradable Plastics

Rod R. Alire, Chief Scientist - FP International

http://www.fpintl.com/
September 8, 2009

Interest in biodegradable disposable plastic items has steadily grown over the last
decade. Disposable packaging materials used to ship and protect purchased items as
well as disposable containers used for food and drink are of special interest. The idea
that one time use items can be disposed of with the peace of mind, that they will not
remain for centuries in a landfill, or as litter, is one of the tenets driving the recent
interest in “green” technologies and lifestyles. With packaging materials, the reduction in
usage of raw materials, re-use and recycling is of course the best route to sustainable
lifestyle. However, for various reasons, in practice, much of the material ends up being
discarded to a landfill or accidentally shows up as litter. For these instances, it is
advantageous to have a plastic material that would biodegrade when exposed to
environments where other biodegradable materials are undergoing decay.

What is Biodegradable?
Biodegradation is degradation caused by biological activity, particularly by enzyme
action leading to significant changes in the material’s chemical structure. In essence,
biodegradable plastics should breakdown cleanly, in a defined time period, to simple
molecules found in the environment such as carbon dioxide and water. The American
Society of Testing and Materials (ASTM) defines ‘biodegradability’ as:

“capable of undergoing decomposition into carbon dioxide, methane, water, inorganic

compounds, or biomass in which the predominant mechanism is the enzymatic action of
microorganisms, that can be measured by standardized tests in a specified period of
time, reflecting available disposal conditions.”

During this process of biodegradation, the large molecules of the substance are
transformed into smaller compounds by enzymes and acids that are naturally produced

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by microorganisms. Once the molecules are reduced to a suitable size, the substances
can be absorbed through the organism cell walls where they are metabolized for energy.
Most naturally occurring materials such as yard waste, food scraps, etc., contain these
large molecules and biodegrade in this way.

Aerobic and Anaerobic Biodegradation

Aerobic biodegradation is the breakdown of an organic substance by microorganisms in
the presence of oxygen. Almost all organic materials can be metabolized in an oxidative
environment by aerobic organisms. The organism has secreted enzymes that
breakdown substances into smaller organic molecules which are then absorbed into the
cells of the microbes and used for cellular respiration. During the respiration process,
the organic molecules absorbed into the cells are broken down in steps, where a
molecule known as adenosine-5’- triphosphate (ATP) is used to store and transport
energy for cells, for life processes such motility and cell division. In biochemistry this
chemical reaction sequence is known as Electron Chain Transfer. In the case of aerobic
metabolism, oxygen is used at the end of the chain as the final electron acceptor,
producing the main byproducts of carbon dioxide and water.

Composting is a well known and common use of aerobic biodegradation, during which
the volume of organic material is typically reduced by about 50%, where the remaining,
slow-decaying humus material left over can be used as a rich planting medium. The
ASTM defines a compostable plastic material as being:

“capable of biological decomposition in a compost site as part of an available program,

such that the plastic is not visually distinguishable and break down to carbon dioxide,
water inorganic compounds and biomass at a rate consistent with known compostable
materials (e.g. cellulose).”

The biomass material referred to here is humus. The bioactivity in active compost will
generate heat that further enhances the rate of microbial growth and metabolism.
However, for the purpose of the ASTM definition, the available program is an industrial
compost facility where heat and moisture are artificially added to the mass to maximize

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the degradation rate. As we will see, this artificial environment becomes critical for
degradation of some biodegradable plastic materials.

Anaerobic biodegradation occurs in the absence of oxygen where anaerobic microbes

are dominant. In the absence of oxygen the organism must use some other atom as the
final electron acceptor. Hydrogen, methane, nitrogen and sulfur are common along with
oxidizing minerals. Thus, the effluent from anaerobic digestion is biogas, consisting of
mostly methane and carbon dioxide, with trace gasses such as ammonia and hydrogen
sulfide. Often, the complete digestion will require several different types of bacteria
where one type partially processes the waste to a point where another bacterium strain
takes over (4). Most biodegradation of solid waste in landfill occurs under anaerobic
conditions by design because it is typically much slower than aerobic degradation.

Most biodegradable substances come from plant and animal matter, or from artificial
materials that are very similar in molecular structure to these naturally occurring
substances. As the naturally occurring substances evolved, microorganisms also
evolved to use the substances as a food source: the carbon in particular, used as a
building block for life-sustaining compounds. Simple sugars are readily absorbed into
the cell to be metabolized. However, larger and more complex molecules such as
starches, proteins and cellulose, require enzymes and acids to reduce their size enough
to be absorbed. Living organisms have developed the ability to secrete specific
digestive compounds so as to best utilize the available food supply. For example, the
enzyme amylase, found in human saliva, is used to breakdown long-chain starch
molecules into and smaller simple sugars.

For microorganisms, this adaptive process can be applied to other, more complex
carbon containing compounds in crude oil. This type of microbial biodegradation has
been demonstrated for hydrocarbons derived from petroleum (10)

Biodegradable Plastic Materials

Currently available degradable plastic materials can be broken down into two main
groups:

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 1. Polyester Polymers
2. Synergistic and Hybrid Polymers

The Polyesters
When one thinks of polyesters in general, the polymers that come to mind are very
durable with good physical and mechanical properties. A good example is polyethylene
terephthalate (PET). This polymer is strong, abrasion and stain resistant, so it can be a
good choice for carpeting and clothing. It also has good gas barrier properties which
make it ideal for soda bottles. These polymers, which are also resistant to
biodegradation, typically contain a large number of six-carbon rings in their molecular
structure. In chemistry, compounds containing these rings are known as aromatic
compounds.

Biodegradable polyesters which do not contain six-carbon rings are known as aliphatic
polyesters. They will typically react with moisture at elevated temperatures to
breakdown the long polymer chains. This process, called chemical hydrolysis, reduces
the higher molecular weight polymer to much smaller hydrocarbon compounds. The
resulting molecules can then be absorbed by microorganisms and metabolized for
energy. Since it is a chemical reaction, the hydrolysis occurs at a much higher rate than
one would expect for a purely biological process, and as a result, relatively quick
degradation is observed.

Aliphatic polyesters have attracted interest as biodegradable plastic materials; however

they typically have poor physical and mechanical properties (3) like strength, flexibility,
heat resistance, etc. Some common biodegradable polyester polymers in commercial
use include poly(caprolactone) (PCL), poly(glycolic acid) (PGA) and poly(butylene
succinate) (PBS). These are synthetic polymers, made from petroleum-based, raw
materials, and like most biodegradable polyesters have inferior mechanical properties
e.g. low heat deflection temperature and low elongation failure (brittle). They will also
begin to hydrolyze at modest temperatures in the presence of moisture, rapidly losing
molecular weight and further decreasing mechanical properties. Although expensive to
make, these biodegradable polymers are ideal for use in specialized, high margin
applications such as medical devices (e.g. dissolving, drug delivery systems, tissue
engineering scaffolds and bone repair etc.).(2)

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Another well known aliphatic polyester is poly(lactic acid). PLA is a synthetic polymer
made from fermented sugars extracted primarily from food crops such as corn, beets or
sugarcane. The resulting lactic acid monomer is chemically processed and then
polymerized, in the presence of a metal catalyst, to form the high molecular weight
plastic material. Like the petroleum-based biodegradable polyesters, PLA has many of
the same undesirable mechanical properties, such as low heat deflection temperature.
The polymer is also very brittle and has a low-melt strength leading to difficulty in
processing. Consequently, most commercial applications using PLA require a synthetic
rubber and/or acrylic additive to compensate for these deficiencies.

Degradation of PLA occurs quickly through a multistep process (4) of chemical

depolymerization, followed by dissolution of the intermediate lactic acid in the presence
of moisture, and the absorption into the cells of microorganisms with subsequent
metabolization. Initiation of this chain of events typically occurs at elevated
temperatures (above heat deflection temperatures), such as conditions existing in an
industrial compost operation. The relatively fast chemical reaction at the beginning of the
chain of events explains the surprisingly quick degradation of polymer in an industrial
compost environment. This mechanism of chemical attack followed by cell metabolism
does not meet the true definition of a biodegradable material inasmuch as biological
activity is not required for the initial breakup of the material. In low temperature aerobic
or anaerobic environments where initial hydrolysis occurs slowly, biodegradation of PLA
also proceeds very slowly if at all.

Another family of biodegradable polyesters, which could in a way be viewed as more

complex extensions of the molecular structure of PLA, is known as polyhydroxy
alkanoates (PHA’s). Intriguingly, PHA’s are natural polymers also derived from plant
sugars but are synthesized within the bacteria themselves. The PHA’s are
manufactured and used as carbon storage in the cells(6), similar to the way the human
body stores fat to be used as an emergency food source.

One of the more notable polymers in this class is polyhydroxy butyrate (PHB), and like
the synthetic aliphatic polyesters, it has the same poor physical and mechanical
properties, and an additional disadvantage of being quite expensive. A cousin to PHB,

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which is actually a copolymer, was developed to help improve these deficient properties.
This co-polyester is known as polyhydroxy butyrate-valarate (PHBV) and has much
better, and more useful, thermoplastic properties that are similar to polypropylene(5).
Since these materials are produced by microorganisms as an emergency food source,
they are, by design, easily biodegradable by direct enzymatic action of microorganisms,
and don’t necessarily require the chemical hydrolysis reaction step first. It has been
shown that bacterially produced PHB/PHV (92/8 w/w) deteriorated nearly to completion
within 20 days of cultivation by anaerobic digested sludge, while synthetic aliphatic
polymers such as PLA, PBS, and poly(butylene succinate adipiate) (PBSA) did not
degrade at all in 100 days (1).

For degradable polyesters, the best improvement in physical properties is obtained by

synthetically creating a polyester copolymer using both aliphatic and aromatic groups.
These are typically derived from oil-based raw materials such as 1,4-butanediol, adipic
acid, and terephthalic acid (7). Using this technique, the polymer can be tailored to
balance the excellent physical and mechanical characteristics of the aromatic polyester
groups with the degradation and subsequent mineralization of the aliphatic groups.
These polymers are also readily mixable with pure aliphatic polyesters like PLA, or
natural polymer like cellulose, to form a hybrid, degradable polymer with improved
performance.

Synergistic or Hybrid Polymers

Synergistic polymers are typically intimate mixtures of oil-based and naturally occurring
polymers where the two have some chemical affinity for each other. When mixed, there
is intimate contact between the two polymer chains so as to create a homogenous single
phase. In other words, once mixed they could not be mechanically separated. This is
somewhat akin to mixing gelatin powder with hot water to form a single uniform
substance, once cooled.

A good example of a commercial, synergistic, biodegradable material is Thermoplastic

Starch (TPS). The key to this blend of the two natural starch polymers, amylose and
amylopectin, and the synthetic polymer, polyvinyl alcohol (PVOH), is their natural affinity
to each other, due to the large number of hydroxyl (OH) groups present in the
compounds. This hybrid can be made into foamed articles, plastic films or molded parts

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such as cutlery. Generational adaptations that occur during the digestion of the familiar
starch groups quickly begin to breakdown the synthetic PVOH chains.

The intimate mixing of the natural and synthetic polymers can be taken one step further:
where the attraction of the synthetic and natural polymers is enhanced by grafting other
chemically compatible groups along the chains of the natural and/or synthetic polymers.
As with the PVOH, this technique enhances biodegradation through generational
adaptation which can be initiated with relatively small additions of natural polymers. To
illustrate how this could be possible, it has been shown that polyethylene will biodegrade
via a monooxygense enzyme pathway (9). Initiation of the process begins with the
formation of a biofilm on the surface of the polymer, which is facilitated by the inclusion
of the compatible natural polymers. These films of microorganisms have been shown to
efficiently biodegrade petroleum based polymers (8).

Low-level synergistic enhancement does not materially impact the physical and
mechanical properties of the original synthetic polymer. Therefore, the product
applications are not restricted beyond what would normally be expected for the un-
amended polymer. Since the additive itself will not degrade the polymer or affect
processing, the ability for recycling or reuse of the plastic article will be unaffected.
Unintended degradation will not occur since the initial colonization requires an
environment where existing biodegradation is occurring or would normally be expected
to occur, either aerobic or anaerobic. Additional heat is not required, and no chemical,
polymer-chain weight reduction process is needed beyond the enzymatic action of the
microorganisms.

Conclusion
For the choice of materials to be used in the manufacture of a more environmentally
friendly packaging material, the criteria needs to take into account business
considerations and strategies, while addressing environmental concerns related to the
life cycle of the packaging. The primary purpose of the packaging material is to protect
the items being shipped from damage via impact or abrasion, and therefore protection
should be the first consideration. The material will also need to perform in largely
uncontrolled, ambient conditions of heat and humidity; thus, the next consideration
should be given to the products’ possible end-of-life scenarios. The scenarios include

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disposal in landfills, litter, recycle, etc. Finally, material costs need to meet market
criteria.

Conventional polymer technologies have been able to tailor materials that can meet the
market need of both cost and performance. There is infrastructure in place for recycling
and/or re-use of many of these materials, which is the most desirable destination in the
life cycle of the packaging product. With inclusion of a synergistic additive, such as that
used by FP International, the materials would also be well-suited for the less desirable
destinations, such as landfills.

The other biodegradable polymer options have no recycle infrastructure, and could
possibly be viewed as having been designed to be thrown out. However, the fact that
many of these polymers, like PLA, are limited to biodegradation in only commercial
compost facilities, further decreases the potential for a desirable end-of-life scenario.
Moreover, while the bacterially produced polyesters (PHB/PHV) would biodegrade in a
more general disposal scenario, they are particularly cost-prohibitive for most packaging
applications.

In addition to sustainable choices in materials for FP International’s products, FP has

ongoing programs for reduction of raw material and energy usage, recycling, increased
production efficiencies, efficient product design and increased recycled, raw material
usage.

About the Author

Rod Alire is Chief Scientist for FP International. Mr. Alire carries more than 20 years
experience in polymer processing with particular expertise in polymeric foam and film
extrusion processes. His projects have emphasized environmental impact mitigation
and sustainability through new product design and manufacturing technologies. By Mr.
Alire’s development of a theoretical model for mass transport phenomena and foam
expansion behavior in polystyrene packaging material production, FP International was
able to reduce the usage of raw materials and density of the products being produced.

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In order to replace the use of CFC’s – chlorofluorocarbon, (known to be harmful to the
ozone and environment), Mr. Alire designed and built a high pressure, foaming agent
metering and delivery system for polymer foam extrusion. Also, he developed polyolefin
polymer blends and a blown film process for production of PMOS (products
manufactured on-site) air bag materials. These airbags are 99% air, since they can be
manually deflated or popped, they also reduce the size of materials produced for
recycling. Also, the size of the film air cushion materials takes less space to ship, thus
less cost and lowers the use of trucks (lowering gas use and truck emissions).
Currently, Mr. Alire is working to increase the strength and mechanical property of the
film itself, in order to produce film which uses less material.

About FP International
FP International, incorporated in 1967 is headquartered in Redwood City, Calif., and is
an award-winning manufacturer of innovative protective packaging products and
packaging systems. The company’s products include packaging-made-on-site (PMOS),
bubble wrapping, packing peanuts, biodegradable packaging, sustainable packaging,
kraft bubble mailers, eco friendly packaging, void fill, environmentally friendly packaging,
loose fill, packaging popcorn and inflatable packaging. Our Flag ship products include
Green Family 100 percent biodegradable packaging Super 8® loosefill and CELL-O®
inflatable packaging air cushions. They are worldwide leaders in eco friendly packaging.
Their instant air cushion packaging, bubble wrapping systems create a smaller carbon
footprint and cut costs for customers. The company also designs and installs custom
dispensing storage systems for air cushions and loosefill. For more information, visit <a
http://www.fpintl.com, http://www.minipakr.com or call 800.888.3725 or 650.261.5300.

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References

1. Shin et al. in Nolan – ITU; ‘Environment Australia, Biodegradable Plastics –

Developments and Environmental Impacts’ (2002)

2. Yoshito Ikada, Hideto Tsuji, ‘Biodegradable polyesters for medical and ecological
applications’, macromol. Rapid Commun. Vol. 21, (1999).

3. Yiwang Chen, Licheng Tan, Lie Chen, Yan Yang and Xiaofeng Wang, ‘Study on
biodegradable aromatic/aliphatic copolyesters’, Brazilian Journal of Chemical
Engineering, Vol. 25, No. 2 (2008).

4. Dunja Manal Abou Zeid, ‘Anaerobic Biodegradation of Natural and Synthetic

Polyesters’, Dissertation, Von der Gemeinsamen Naturwissenschaftlichen
Fakultat der Technisschen Universitat Carolo-Wilhemina zu Braunschweig
(2001).

5. Yon Jia, Wei Yuan, Jola Wodzinska, Chung Park, Anthony J. Sinskey, JoAnne
Stubbe, ’Mechanistic Studies on Class I Polyhydroxybutyrate (PHB) Synthase
from Ralstonia eutropha: Class I and III Synthases Share a Similar Catalytic
Mechanism’, Biochemistry, (2001), 40.

6. Sung-Eun Lee, Qing X.Li, Jian Yu, ‘Diverse protein regulations on PHA formation
in Ralstonia eutropha on short chain organic acids’, International Journal of
Biological Sciences, (2009), 5.

7. Ilona Kleeberg, Claudia Hetz, Feiner Michael Kroppenstedt, Rolf-Joachim Muller,

Wolf-Dieter Deckwer, ‘Biodegradation of Aliphatic-Aromatic Co-polyesters by
Thermomonaspora fusca and Other Thermophilic Compost Isolates’, Applied and
Environmental Microbiology, Vol. 64, No. 5, (1998).

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 8. Gamini Seneviratne, N.S. Tennakoon, et al. ‘Polyethylene biodegradation by a
developed Penicillium-Bacillus biofilm’, Current Science, Vol. 90, No 1, (2006).

9. van Beilen in Seneviratne

10. Okerentugbea in Seneviratne

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