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Bioplastics
plastics of the future ?
Dr Jrme Peydecastaing
May 2013

The context
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Global demand for plastics
in 2011: 205 million tonnes (BPF)


Traditional plastics are:
Recyclable
Versatile
Lightweight
Moisture resistant
Durable
Strong
Relatively inexpensive
It can be chemical resistant, clear or opaque.
These are wonderful useful qualities, and plastic
plays many important roles in life.
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But Traditional plastics are also:
Derived from non-renewable, fossil sources.
Responsible for global warming when burned.
Non-biodegradable, tend to accumulate.
Responsible for pollution: To be recycle, plastics have to be
collected.
Recycling

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Recycling

Source: Wrap
Non-Biodegradability of plastics
600-1000 years?
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In this context
Renewable resources are becoming a more viable
and promising alternative for the plastics industry.
What about biodegradable plastics ?

R&D activities on
bioplastics
Ideal scenario and marketing
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Definitions
Definitions
Bio-based material:
an engineering material made from substances derived from
living matter. (!"#$ &'('')
Biopolymer:
any polymeric chemical manufactured by a living organism,
as proteins and polysaccharides.
such a chemical prepared by laboratory synthesis.
Bioplastics:
The term "bioplastics" refers to a biodegradable plastics and/
or plastics derived from renewable resources (the definition
from European Bioplastics)

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Thermoplastics and thermosets
Thermoplastic
Thermoset
Temperature
Rubbery state
Glassy state
Tg
Transition
area
Tg: glass transition
temperature
Low molecular
agitation
breakable
polymer
High molecular
agitation
Thermoplasticity

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Thermoplastics and thermosets
The bioplastics
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Bioplastics
Natural polymers from biomass (starch, modified
cellulose).
Polymers obtained by microbial production (PHA).
Synthetic polymers whose monomers are obtained from
biomass (PLA).
Synthetic polymers whose monomers and polymers are
obtained conventionally by chemical synthesis (PCL,
aliphatic and aromatic copolyesters).
Overview of bio-derived feedstock and polymers
Natural polymers Synthetic polymers
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Natural polymers
Agricultural feedstock
Natural polymers: Starch
Second largest biomass on earth, after cellulose
The predominant food reserve substance in plants
where it occurs as starch granules
Seeds (e.g. peas, grains, beans)
Roots, tubers, stems (e.g. potato, tapioca, pineapple)
Fruits (e.g. plantain bananas)
Leaves (e.g. tobacco)
One of our main carbohydrate source
Primary use in foods
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Natural polymers: Starch (C
6
H
10
O
5
)
n

Starch is complex made of polysaccharides whose repeating
glucose units are linked by !1!4 glycosidic linkage.
The length of the starch chain will vary between 500-20,000
glucose units.
There are actually two types of starch molecules:
Amylose
Amylopectin.
Natural polymers: Starch
Amylose
Amylopectin
Starch
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+
MILLING
STARCH
AMORPHOUS
AMYLOSE AND
AMYLOPECTINE
COMPLEXED
STARCH
Destructuration
Chemical modification
POLYMERIC
COMPLEXING AGENTS
Cereals, tubers, !
Final product
Emerging application areas
! COATED PAPER
! AGRICULTURE MULCH FILM
! SHOPPING BAGS
! FOOD WASTE FILMS AND BAGS
! CONSUMER PACKAGING MATERIALS
! LANDFILL COVER FILMS
! OTHER APPLICATIONS
Natural polymers: Starch
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Natural polymers: Cellulose
Natural polymers: Cellulose
Why modify cellulose ?
Amorphous region Crystalline region
O
OH
OH
HO
O
OH
HO
OH
O
Cellulose is not a thermoplastic
(!-1,4-glycosidic linkage)
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Natural polymers: Cellulose acetate
Raw materials:
Wood pulp: high-quality (>95% !-cellulose and
1000<DP<2500)
Cotton : high purity raw material with !-cellulose content
(>99%) and 1000<DP<7000

Cellulose acetate:
1865
Natural polymers: Cellulose acetate
Two categories of processes :
> Acetylation in homogeneous system
glacial acetic acid
methylene chloride
> Acetylation in heteregeneous system
CCl
4

Toluene
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Natural polymers: Cellulose acetate
Thermoplastic materials.
Transparency, high clarity.
Toughness.
Moisture resistance.
Dimensional stability.
Slowness to burn.
Non Biodegradable.
Natural polymers: Cellulose esters
Thermoplasticity
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Natural polymers: New concept
Natural polymers
Microbial origine
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Bacterial bioplastics: PHAs
Polyesters accumulated inside microbial cells as
carbon & energy source storage.
PHA: White patches in microorganism
Bacterial bioplastics: PHAs
Produced under conditions of Low limiting nutrients (P, S, N, O) and
Excess carbon.
~250 different bacteria have been found to produce some form of
PHAs.
PHA R
PHB - CH
3
PHV -CH
2
CH
3
PHBV (Biopol) - CH
3
& CH
2
CH
3
PHBHx -CH
3
& - CH
2
CH
2
CH
3
PHBO -CH
3
& -(CH
2
)
4
CH
3

O
R
OH
O
H
x
n
PHA structure
R = Hydrocarbon (up to C13)
x = 1 to 3 or more
N = 100 30 000
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Bacterial bioplastics: Recovery of PHA
PHA producing microorganisms stained with Sudan
black or Nile blue
Cells separated out by centrifugation or filtration
PHA is recovered using solvents (chloroform) to
break cell wall & extract polymer
Purification of polymer
Bacterial bioplastics: PHAs
Advantages
" Biodegradable
" Eco-friendly synthesis
" Renewable resource
" Good mechanical
properties
" Water resistant
Inconvenients
" Poor interaction with
fibers
" Extraction process
" Narrow processing
window
" Thermal degradation
(185C)
" Brittleness
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Bacterial bioplastics: PHB
Discovered by French
microbiologist Maurice
Lemoigne in 1923.
Next generation PHB will
come from Transgenic
plants/micro-organisms
Typical cost ranges from
5-6"/kg
Ref: Marchessualt, R. H.; TRIP, 1994, 4, 163

Synthetic polymers
Biotechnological origin
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PLA is not a polyacid,
but rather a polyester
Polylactic acid (PLA)
PLA are thermoplastic aliphatic polyester made from
!-hydroxy acids, derived from renewable resources, such as:
corn starch (in USA),
tapioca products (roots, chips or starch mostly in Asia),
sugarcanes (in the rest of world).
Catalyzer: Stannous octonate or tin(II) chloride
Polylactic acid (PLA)
Bacterial fermentation is used to produce lactic acid.
Two lactic acid molecules undergo a single esterfication and
then catalytically cyclized to make a cyclic lactide ester.
PLA of high molecular weight is produced from the dilactate
ester by ring-opening polymerization.
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Lactic Acid
Fermentation
Unrefined
Dextrose
Polymer
Production
PLA
Monomer
Production
Lactide
Corn
Starch
Sugar
Production
PLA Manufacturing Overview
PLA rigid Packaging
Sources: Novamont; Coopbox; Whole Foods Market; NatureWorks
TM
Low glass transition
temperature

PLA materials cannot
hold hot liquids.
However, much
research is devoted to
developing a heat
resistant PLA
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Polylactic acid (PLA)
PLA i s biodegradable (short-term packagi ng) and
biocompatible (biomedical applications).
Good mechanical properties (can be comparable to PET)
PLA can be degraded by abiotic degradation. In a second
step, the enzymes degrade the residual oligomers till final
mineralization.
PLA is an environmentally friendly material when lactic acid
is produced from biomass by fermentation,.
PLA production leads to a growing demand for corn,
competing bioethanol production and corn-dependent
commodities.
Synthetic polymers
Petroleum / natural based
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Fossil-based bioplastics
Synthetic biodegradable polymers whose monomers and
polymers are obtained conventionally by chemical synthesis.
Less than 1% of the bioplastics in 2011.
Polycaprolactone (PCL) Polyesteramide (PEA)
Aliphatic copolyesters (PBS) Aromatic copolyesters (PBT)
Bio-based synthetic plastics
Synthetic polymers non biodegradable usually
obtained from fossil resources.
They are considered as bioplastics when derived
from renewable resources.
Polyethylene
PE
Polyvinyl chloride
PVC
!
Polypropylene
PP
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Bark of pine, corn sheets, orange peels, potato skins, oats# other
nonfood resources
Biological and chemical process
PET (identical to fossil sourced)
Experimental production in 2012
PepsiCo
A bottle 100% bio-based
Biorefineries of the future will integrate:
Production
End-Uses

Products
Fuels
Plastics
Solvents
Chemical Intermediates
Phenolics
Adhesives
Hydraulic Fluids
Fatty acids
Carbon black
Paints
Dyes, Pigments, and Ink
Detergents
Pulp & Paper products
Horticultural products
Fiber boards
Solvents
Adhesives
Plastic filler
Abrasives

Fuel
Power
Processing
- Acid/enzymatic
- hydrolysis
- Fermentation
- Bioconversion
- Chemical Conversion
- Gasification
- Combustion
- Pulping
Plant Science
- Wood, trees
- Grasses
- Energy crops
- Agricultural
Residues
- Genomics
- Enzymes
- Metabolism
- Composition
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Biodegradability
Concept
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Definitions
Biodegradation: degradation caused by the action of
microorganisms (3 steps):
Biofragmentation of the material
Bioassimilation
mineralisation in CO
2
, H
2
O and/or CH
4
and a new biomass

A material is called biodegradable with respect to specific
environmental conditions if it undergoes biodegradation to a
specified extent, within a given time, measured by standard
test methods.
Compostable plastic is one that meets all scientifically
recognized standards of compostabilty regardless of the origin of
carbon.
Compostable plastic is always biodegradable
Biodegradable plastic is not always compostable
What is compostable plastic?
European standard is EN 13432,
USA standard is ASTM D6400.
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Macroscopic and microscopic scales
Photodegradable plastics can break down to small fragments and lose
structure but small fragments are not degradable.
Semidegradable plastics often contain starch, cellulose and polyethylene.
Dramactic impact on the planet
ASTM D6400 Main Factors
1. Mineralization
> 90 percent conversion to carbon dioxide, water
and biomass through the action of microorganisms
> The same rate of degradation as other organic
waste (ie. leaves, grass ...)
> Time period of 180 days or less
2. Fragmentation
> Not more than 10% of the original dry weight of test material shall
fail to pass through a 2 mm fraction sieve.
3. The impact on the environment
> No negative impact on flora and fauna
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ISO
(Global)
JIS
(Japan)
ASTM
(USA)
CEN
(UE + AELE)
AFNOR
(France)
DIN
(Germany)
BS (UK) #.
#
New ISO 17088 for compostable plastics (2012)
So many Standards
2 major axis of studies:
- measurement in simulated environment (laboratory tests)
- measurement in real environment
Sturm test / Enzyme
assay / Clear-zone test
Mixed cultures
Defined media
Soil / Compost
Landfill / Water
External
conditions
Laboratory
test systems
Mixed cultures
Defined media
Defined media
Field
tests
Simulation
tests
Defined
conditions
Transferability to practice
Analytical accessibility
Soil / Compost
Landfill / Water
The assessment of biodegradability
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Pressurized air Air (no CO
2
) Air outlet
Plastic
+ liquid
O2
consumption
measurement
Titration
Gas chromatography
FTIR or NIR
Clean air (no CO
2
)
producer
Fermenter Measurement system
Plastic
+ liquid
CO
2
production
measurement
Laboratory tests
0
100
200
0 5 10 15 20 25 30 35 40 45
Time (Days)
T
o
t
a
l

C
O
2

p
r
o
d
u
c
t
i
o
n

(
g
)
Cellulose
Blank - Inoculum
= net CO2 production
= biodegradation
EN 13432: Biodegradability
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Bioplastics and biodegradability

Generally accepted ideas
Bioplastics are biodegradable
Petrochemical plastics are not biodegradable
Bioplastics and biodegradability
!"#$%&'()*&: renewable or noL renewable
+),&$-).: blodegradable or noL blodegradable
lasucs: 263 M Lons (2010) - lasucs Lurope
8loplasucs: 0.724 M Lons
blodegradable (non renewable resources) 428 000 L
plasucs from renewable resources 296 000 L
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Bioplastics market
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uevelopmenL of bloplasucs Lhrough hlsLory
Renewable resources
Petrochemical raw materials
Degradable
Non-
degradable
Based on
renewable
resources
Bio-degradable
V.
BioPE, BioPA
BioPU, BioPP, BioPVC
I.
Cellulose acetate
Rubber#
IV.
Starch blends
PHA
PLA
Regenerated cellulose
#
III.
Polycaprolactone
Polyvinyl alcohols
Polyesters
#
II.
Polyethylene
Polypropylene
Polyvynil chloride
#
Projected Bioplastics trends
Production capacity of bio-based plastics is projected to increase
from 360,000 tonnes in 2007 to about 2.3 MILLION tonnes by 2013.
(European Bioplastics)
Global production capacity for PLA (Polylactic Acid) is expected to be
800,000 tonnes by 2020. (Nova Institute 2012)
USA demand for bioplastics predicted to grow at 20% through 2016
to reach 249,000 tonnes valued at "552 million. (Freedonia Group 2012)
Biodegradable account for the majority of bioplastics in 2011 but non-
biodegradable will grow to 40% of the market by 2021.
Major growth will be bio-based Polyethylene as well as bio-based
PET and PVC.
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European Union
Plastics: 57 M tons
100% from biomass
34% Europe lands
limagrain
Non food biomass (Food waste) has to be used for bioplasticcs.
Compostable Bioplastics Do Not Yet
meet the Needs for Durables


Starch Blends
Hydrolytic stability
Distortion Temp
Vapor Transmission
Shelf Life
PLA
Hydrolytic Stability
Distortion Temp
(amorphous)
Vapor Transmission
Shelf Life
Impact Resistance
Melt Strength
PHAS
Hydrolytic Stability
Shelf Life
Processability
Melt Strength
Economics

.
.

.
.

..
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Braskem
Dow/Crystalsev
DuPont
Arkema
BASF
Rohm & Haas
Dow, Cargill
NatureWorks LLC
HDPE, LLDPE, PP
HDPE
Nylon
Nylon
Nylon
Acrylics
Soy based urethanes
PLA Blends
Degradable
Durable
Novamont
NatureWorks
Metabolix
DSM
Origo (starch)
PLA
PHAs
PHAS
##########################################
##########################################
WHO? WHAT?
Biobased Leaders Tomorrow?
Cost (2010) Leaders Commercial products
1,5-3 "/kg Starch
# NOVAMONT
# RODENBURG
# NATIONAL STARCH
# BIOTEC
# Mater-Bi
# Solanyl
# Ecofoam
5-6 "/kg **
3-4 "/kg PLA
PHA
#
CARGILL # Nature Works
# METABOLIX
# PROCTER&GAMBLE
# Biopol
# Nodax
# BASF # EcoFlex Poyester
Traditional plastics cost (PE, PP, PVC...)
1"/kg
3-5 "/kg **
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The future for bioplastics will depend on!.
Expanding from Single Use Compostable to Durable
Applications
Focus on Life Cycle Assessment
Transitioning from Oil Based to Renewable Feedstock
Addressing Issues Sociological, Environmental & Political
Composting/Recycling Infrastructure Developments
What about modified bio-materials ?
Jerome.Peydecastaing@ensiacet.fr
www.chimieagroindustrielle.fr
Thank you for your attention
Any questions ?
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