This document provides an introduction and overview of bioplastics. It defines key terms like biodegradable, biobased, and standards for compostability. The drivers for bioplastics include being renewable, having reduced environmental impact, and addressing end-of-life disposal issues. Projections show strong growth in bioplastics production and demand over the next 5 years. While compostable bioplastics are growing, durable bioplastic applications are expected to account for nearly 40% of the market by 2011 to address performance shortcomings of compostable plastics. Emerging technologies may expand bioplastic uses in electronics and automotive industries.

1. Introduction To Bioplastics
Dr. Jim Lunt

2. Basic Definitions for Bioplastics.
Drivers for Bioplastics.
Growth Projections and Market Trends.
The Evolving Biobased ―Landscape.‖
Performance Issues for Today’s Bioplastics.
Emerging Technologies.
Conclusions.
Presentation Outline

3. Basic Definitions for Bioplastics
Terminology
Standards
Measurements

4. What are Biodegradable Plastics?
Biodegradable or Compostable Plastics are
those which meet all scientifically recognized
norms for biodegradability and compostability
of plastics and plastic products independent
of their carbon origin.
In Europe, the composting standard is
EN 13432 and in the USA ASTM D6400.

5. ASTM D6400 Standard Criteria For
Compostability
1. Mineralization
• At least 90 percent conversion to carbon dioxide, water
and biomass via microbial assimilation.
• Occurs at the same rate as natural materials
(i.e. leaves, grass food scraps.)
• Occurs within a time period of 180 days or less.
2. Disintegration
• Less than 10 percent of test material remains on a 2mm
sieve.
3. Safety
• No impact on plants, using OECD Guide 208.
• Regulated (heavy metals less than 50 percent of EPA
prescribed threshold.)

6. Embrittlement
begins
Complete
Fragmentation
Polymer Hydrolysis
Lactic acid and Oligomers
Biodegradation
0
10 20 30 40
10,000
30,000
50,000
70,000
0
20
40
60
80
100
Time (Days)
Num. Avg. Mol. Wt. (Mn) % CO2 Evolved
% CO2
Mn
Biodegradation Mechanism For PLA
(In Compost At 60oC)

7. Products that are composed wholly or
significantly of biological ingredients
—renewable plant, animal, marine or
forestry materials.
Does not consider if plastics are
compostable or durable.
Does not refer to any standards of
measurement.
USDA Definition of Biobased Products

8. To be classified as ―biobased,‖ the material
must be organic and contain some
percentage of recently fixed (new) carbon
found in biological resources or crops.
This definition is the basis of ASTM D6866.
Uses C14 content measurement.
Measurement of Biobased Content

9. Measurement of Biobased Content

10. Biobased Plastics
Major focus is on the ―origin of life‖
or where did the carbon come from (ASTM D6866).
Uses C14 content measurement.
Biodegradable (Compostable) Plastics
Focus is on ―end of life or disposal.‖
Independent of Carbon Source Standards
EN 13432 and ASTM D6400.
These two classes are, however,
not mutually exclusive.
Biobased & Biodegradable

11. Alternative Disposal Initiatives
 BIOCOR in the USA to establish an infrastructure to allow
collection of PLA postconsumer and industrial waste.
 Primarily, this appears to be in response to the resistance
by bottle recyclers to accept PLA due to contamination
concerns, but will also allow a potentially more sustainable
business model.
 This initiative is still in its infancy and will not materially
affect PLA growth in the near term.

12. Renewable resource versus oil based.
Reduced environmental impact.
Concerns about human health.
End-of-Life disposal issues – Landfill.
Legislative initiatives.
Drivers for Bioplastics

13. Oil Versus Corn Price
Courtesy Gevo

14. Oil Carbon V Corn Carbon Price
% Carbon in oil = 84% based on isooctane
There are several grades of crude oil,
Assuming 35.6° API, is 847 kg / m3
and a barrel is 0.159 m3 it would be 134 kg or 295.4 lbs
A US barrel of oil is 42 gal.
Cost of oil based carbon example
$60/(0.84*295.4) = $0.242
% carbon in Dextrose = 40
% dextrose from corn = 65
Weight of a bushel = 56#
Cost of corn based carbon example
$3.50/(56*0.65*0.4) =$0.240

15. Oil Versus Corn Price
1.40
1.90
2.40
2.90
3.40
3.90
4.40
4.90
30.00
40.00
50.00
60.00
70.00
80.00
90.00
100.00
0.05 0.15 0.25 0.35
crude oil cost
corn cost
$Oil/barrel
$Carbon Cost
$Corn/Bu
Cost of Carbon
Oil v Corn Sugar

16. Hull & Fiber
(23%)
•
Starch
(65%)
Germ
(7%)
Gluten Meal
(5%)
Fructose for
Sweeteners
Dextrose for
Fermentation
Feedstocks
Number 2Yellow Dent is used in the USA for Lactic Acid Production
Corn as A Feedstock

17. Typical yields from a bushel of corn (56 pounds) from the wet
mill include:
 31.50 lbs starch
(33.3 lbs sweetener, due to hydrolysis weight gain.)
 1.55 lbs of corn oil.
 13.50 lbs of corn gluten feed.
 2.60 lbs of corn gluten meal.
The value of these by products ranged from $1.35/bu to
$2.95/bu during the period of 2007-2008.
Corn ranged from $3.03/bu to $6.55/bu, resulting in a
computed price for net corn of $1.13/bu to $3.82/bu.
Based on these values, the USDA reports a corn sweetener
(dextrose) cost.
Net Corn Pricing Calculation

18. White Pollution-China

19. Increasing Litter Concerns

20. Health Concerns

21. Legislation Against Petroleum Based Plastics

22. Japan
Government has set a goal that 20% of all plastics
consumed in Japan will be renewably sourced by 2020.
Germany
Ban on land filling solid waste with over 5% organic content.
Biodegradable plastics exempt from the recycling directive until
2012.
Savings of 1.3 €/kg in favor of compostable bioplastics.
Netherlands
Implementing a 40 euro cents/kg tax on PET vs. tax on PLA of 8
euro cents/kg.
USA
Federal Farm Bill - Energy Title 9
Each Federal agency must design a plan to purchase as many
biobased plastics as practically possible. Federal procurement
plan will be based on biobased content, price and performance.
Key Legislative Initiatives for Bioplastics

23. Definition of Sustainability
Sustainability is simply stated as:
“meeting the needs of the present
without compromising the ability
of future generations to meet their
own needs."
BUT…..
How do we achieve and measure
this?

24. How Do We Really Measure
Sustainability?
Life Cycle Analysis - One attempt to
measure sustainability.
Complex and Inputs/Outputs still Debated

25. Life Cycle Analysis
ISO 14040 or ASTM D7075 -LCA involves the
compilation of a comprehensive inventory (Life Cycle
Inventory, or LCI) of relevant inputs and outputs of a
production system.
This means an organized effort to measure specific
input components contributing to the production and
delivery of the material to its end-use application.
In addition, an LCA requires an evaluation and
assessment of the environmental impacts associated
with the processes.

26. 2.02
0.27
0.75
2.52
3.49 3.49
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
2005 2006 2009 ACC Plastics
Europe
Gabi
PEA
kgCO2eq./kgIngeo
Source Data: Ingeo - NatureWorks LLC ; PET: M. Binder, Technical Director, PE Americas;
Ingeo PET
With REC Technology
Improvements
Compared to any of the PET data sets, all of the Ingeo profiles have
a lower contribution to climate change
PLA: Vink E.T.H. et all

27. 50.2
27.2
35.2
69.6
77.8
85.6
0
10
20
30
40
50
60
70
80
90
2005 2006 2009 ACC Plastics
Europe
Gabi
PEA
MJ/kgIngeo
Source Data: Ingeo - NatureWorks LLC ; PET: M. Binder, Technical Director, PE Americas;
Ingeo PET
With REC Technology
Improvements
Compared to any of the PET data sets, all of the Ingeo profiles
have a lower non-renewable energy use
Cradle-to-Pellet Primary Non-renewable
Energy Use
PLA: Vink E.T.H. et all

28. The Food versus Fuel Debate:
• Food Crops V Biomass
• The ―Ripple Effect ―
Use of GMO's
End-of-Life disposal options:
• Compostability
• Recyclability
But There Are Other Issues

29. Projected Biomaterials Trends

30. Global
Demand
for bioplastics
will increase
more than
fourfold to
900,000
tonnes in
2013.
(Freedonia)
Projected Biomaterials Trends

31. Global
Production
of bioplastics
will increase
sixfold to
1.5
million
tonnes
by 2011.
up from 262,000
tonnes in 2007.
(European Bioplastics)
Global
Demand
for bioplastics will
increase more than
fourfold to
900,000
tonnes in
2013.
(Freedonia)
Projected Biomaterials Trends

32. Production
Capacity
of bio-based
plastics is
projected
to increase from
360,000 tons
in 2007 to about
2.3
million tons
by 2013.
(European Bioplastics)
Global
Production
of bioplastics
will increase six
fold to
1.5
million
tons
by 2011.
up from 262,000
tonnes in 2007.
(European Bioplastics)
Global
Demand
for bioplastics
will increase
more than four
fold to
900,000
tons in
2013.
(Freedonia)
Projected Biomaterials Trends

33. Bioplastics will still only be
1% of the approximate 230 million tons
of plastics in use today.
Projected Biomaterials Trends

34. The Evolving Biobased Plastics Landscape

35. Biobased Polymer Capacities
For Major Players
Product Company Location Capacity/mt Price/#
PLA
PLA
PHA’s
PHBH
PHBV
Materbi
Cereplast
HDPE/LDPE
/PP
Natureworks
Hisun
Metabolix
Meridian/Kaneka
Tianan
Novamont
Cereplast
Braskem
USA
China
USA
USA
China
EU
USA
SA
140,000
5,000
300/50,000
(2010)
150,000?
2,000
75,000
25,000
200,000
(2010)
0.85-1.20
1.25
2.50-2.75
n/a
2.40-2.50
2.0-3.0
1.50-2.50
0.80-1.00

36. NatureWorks, Hisun
Novamont
Cereplast
Dupont
Tianjin Bio Green /DSM
Tianan Biologic
Metabolix
Braskem
PLA
Mater-Bi, Origo Bi
Cereplast
BIOMAX (PTT, Plantic)
PHA
PHBV
PHA
Green Polyethylene
The Biobased Leaders Today
………………………………………………………………………………………………………………
………………………………………………………………………………………………………………
WHO? WHAT?

37. Compounded
Biobased Compostable
O
OH
HO
H CH3
L-Lactic Acid
O
OH
HO
H3C
H
D-Lactic Acid
(0.5%)
Polylactic Acid (PLA)
100% Renewable & Compostable
Key Compostable Bioplastics
Starch/PLA/ECOFLEX
…………………….……………………………………………………………

38. Compostable Bioplastics
Second Generation
Poly Hydroxy Alkanoates
(PHA’s

39. Major Bioplastic Packaging Markets
Four Sectors showing significant growth:
1. Compostable, single-use, bags/films.
2. Thermoformed products for food applications.
3. Gift cards.
4. Plastic foams based on soy-based polyols.

40. Plastic Films Market Size
US plastic bag market is estimated by Omni Tech*
to be 68 million tons in 2007.
Growth rate of 15% per year through 2011 to
119 million tons.
*http://soynewuses.org/downloads/reports/DisposalblePlasticsMOS.PDF

41. Major Markets for Biobased Films
Clear wrapping films (blown and cast) for food- and non-food
wrap.
Clear biaxially-orientated film for tamper proof seals and shrink
wrap.
Translucent cast and blown film for:
Trash bags Yard & Garden
Industrial refuse Kitchen and other
Newspaper and magazine wrap Diaper back sheets
Agricultural mulch films
Almost all biobased film applications today are single-use
disposables where compostability is a perceived benefit along
with biobased content.

42. Bioplastic Manufacturers for Film
Applications
Transparent rigid films:
PLA,( NatureWorks LLC.) Cellulose acetate (Innovia)
Translucent flexible films:
Starch/PLA, and/or Ecoflex synthetic polyester
• Materbi, (Novamont)
• Bioplast, (Stanelco / Biotec)
• Ecovio, PLA/ Ecoflex (BASF)
• Ecobras, Starch / Ecoflex (BASF)
• Cereplast Compostables, (Cereplast)
Hydroxy propoxylated starch, (Plantic Technologies)

43. Major Concerns with Bioplastic Films
• Cost / lb. and density v polyethylene /
polypropylene.
• Lack of curbside collection and municipal
composting infrastructure.
• Poor tear propagation.
• Moisture sensitivity for starch based products.
• Controlled degradation times for mulch films.
• Barrier (moisture transmission) for starch and PLA
formulations.
• Low temperature resistance of PLA unless
orientated.

44. Resin OTR WVTR CO2
PLA 38-42 18-22 201
PET (OPET) 3-6.1 1-2.8 15-25
HDPE 130-185 0.3-0.4 400-700
PP 150-800 0.5-0.7 150-650
Nylon 6 2-2.6 16-22 10-12
EVOH 0.01-0.16 1.4-6.5
PVC 4-30 0.9-5.1 4-50
Comparative Gas Transmission Properties

45. Biaxially Orientated PLA

46. Cellulose Acetate

47. Compounded PLA/Starch Blends

48. Braskem
Dow/Crystalsev
DuPont
Arkema
BASF
Rohm & Haas
Dow, Cargill
NatureWorks LLC
HDPE, LLDPE, PP
HDPE
PTT; PBT; Nylon 6,12
Nylon 11,Pebax
Nylon 6,10
Acrylics
Soy based urethanes
PLA Blends
Degradable
Tomorrow’s Biobased Leaders
Durable
Novamont
NatureWorks
Metabolix
DSM
Origo Bio
PLA
PHA’s
PHA’S
………………………………………………………………………………………………………………………
………………………………………………………………………………………………………………………
WHO? WHAT?

49. Continuing lack of infrastructure for use
and disposal of compostable plastics.
Many biobased plastics players too focused on
compostability as the key differentiating asset.
Increasing demand for biobased, semi-durable
and durable products for household goods,
electronics and automotive applications.
Increasing interest and developments in existing
and new monomers from renewable resources.
Why The Change?

50. Increasing demand for biobased, durable products
in electronics and automotive applications.
By 2011 durables are expected to account
for almost 40% of bioplastics –
compared with 12% today.
(European Bioplastics)
Projected Durables Growth

51. Durable Applications are a Reality
Disposables Durables

52. Starch Blends
Hydrolytic stability
Distortion Temp
Vapor Transmission
Shelf Life
Areas of Concern
PLA
Hydrolytic Stability
Distortion Temp
(amorphous)
Vapor Transmission
Shelf Life
Impact Resistance
Melt Strength
PHA’S
Hydrolytic Stability
√
√
Shelf Life
Processability
Melt Strength
Economics
Compostable Bioplastics Do Not Meet
The Needs for Durables
…………………….……………………………..……………
…………………….……………………………..……………
…………………………………………………………………………………………………………………..……………

53. Will Biopolymers Follow the
Traditional Path to Maturity?
BASE POLYMER
ADDITIVES
Fillers/Fibers, Pigments
Lubricants, Mold release agents
MODIFIERS
Impact modifiers, Rheology
modifiers, Plasticizers,
Nucleating agents
BLENDS
Rigid/Flexible
Low/High Temp
COPOLYMERS
Chemical Res., High Heat
Ductility

54. Will Biopolymers Follow the
Traditional Path to Maturity?
BASE POLYMER
(PLA)
ADDITIVES
Talc, Kenaf
MODIFIERS
Acrylics,
Joncryl,
Citroflex, EBS
BLENDS
PLA / Ecoflex
PLA / PHBV,
PLA / PC
COPOLYMERS
Isosorbide
2,5 FDCA
PTT / Nylon 11
Bio Analogs

55. How Will Bioplastics Meet Future
Durable Products Needs?

56. General trends
How Will Bioplastics Meet Future
Durable Products Needs?
• Short Term (1-3years) – Blends of present
generation bioplastics & blends with petro-based
plastics (PP, acrylics, polyamides )

57. General trends
How Will Bioplastics Meet Future
Durable Products Needs?
• Short Term (1-3years) – Blends of present
generation bioplastics & blends with petro based
plastics (PP, acrylics, polyamides )
• Medium Term (3-5 years) – Blends of existing
bioplastics with other biobased plastics
(PTT, nylon 6,10, PBS)

58. General trends
How Will Bioplastics Meet Future
Durables Products Needs?
• Short Term (1-3years) – Blends of present
generation bioplastics & blends with petro based
plastics (PP, acrylics, polyamides)
• Medium Term (3-5 years) – Blends of existing
bioplastics with other biobased plastics
(PTT, nylon 6,10, PBS)
• Longer term (5-10 years) – Biobased plastics
& bioderived conventional plastics?(PET,PE,PP, nylon 6)

59. Improved temperature performance over PLA.
Improved processing window over PHBV.
Wider mechanical property spectrum.
Almost completely renewable-resource based.
Still compostable.

60. Heat Distortion Properties of PHBV/PLA Blends
COURTESY OF PETER HOLLAND BV
• Samples Held up to 12minutes at 100 C
100%PLA
90%PLA/10%PHBV
80%PLA/20%PHBV
70%PLA/30%PHBV
60%PLA/40%PHBV
50%PLA/50%PHBV
2Minutes
•Deformed
12Minutes
•Not
Deformed

61. Sample Load MPa HDT oC
100% PLA 0.45 52.0
90/10 0.45 53.4
80/20 0.45 54.5
70/30 0.45 54.6
60/40 0.45 63.0
50/50 0.45 66.3
Heat Distortion Properties of
PHBV/PLA Blends

62. 1. 10% PHBV / 90% PLA 45.2OC
2. 20% PHBV / 80% PLA 34.0OC
3. 30% PHBV / 70% PLA 33.4OC
4. 40% PHBV / 60% PLA 23.9OC
5. 50% PHBV / 50% PLA 14.7OC
Glass Transitions of PHBV/PLA Blends

63. PHBV/PLA Blended Product

64. Succinic Acid
THF
1,4-Butanediol
Polyurethanes
Aliphatic
Polyesters
Polycarbonates
PBT
Polycarbonate/PBT Blends
Solvents
New monomers
TPE’s
Salt
Replacements
Crop
Growth
Promoters
N-Methyl Pyrolidone
Adipic Acid Hexanediamine
Nylon 6 & 6,6
Other Chemicals and Polymers from Plant
Sugars
Plant Sugars

65. L-KetalsHO
OH
O
O
succinic acid
HO OH
O
3-hydroxypropionic acid
OH
O
NH2
HO
O
glutamic acid
aspartic acid
OH
HO
O
O NH2
HO OH
OH
glycerol
O
OHO
4-hydroxybutyrolactone
itaconic acid
HO
OH
O
O
O
O
OH
levulinic acid
O
O
OH
O
HO
2,5-furandicacboxylic acid
OH OHOH
OH OH
xylitol
OH
OHOH
OH
OH
OH
sorbitol
HO
OH
OH
OH
OH
OH
O
O
glucaric acid
O
O
HO
O
OR
*R=H, alkyl
New Biobased Materials In Development

66. Thermoplastics
Products and Markets
L-Ketals
Plasticizers Polyols
Adhesives
Solvents

67. IsobutyleneIsobutanol
Xylenes and
other aromatics
terephthalic acid
PET
other polymers
Isooctene
Courtesy Gevo
Biobased TPA For PET Under Development

68. Polyethylene from Sugar Cane
Nylon 6 from Lycine
Acrylics from Sugar
Polyurethane Using Soy Based Alcohols
Increasing Synergism with the Biofuels Initiatives
Other Durable Bioplastics Are Appearing

69. Monomers from Sugar / Cellulosic Biomass
Succinic acid (DSM, Bioamber, Roquette, Mitsubishi Chemical
Myriant)
3-hydroxy propionic acid (Cargill, Codexis)
Acrylic acid (Ceres, Rohm & Haas)
Aspartic acid (China)
Levulinic acid (China)
Sorbitol (Cargill, ADM, Roquette)
Ethylene/ethylene glycol (Braskem, India Glycols)
Propylene/propane 1,3 diol (Braskem, DuPont / Tate & Lyle)
Butylene/butane diol (Genomatica)
Lysine/caprolactam (Draths)
Terephthalic acid (Gevo)
Adipic acid
Isoprene (Goodyear, Genenco)
FDCA- Avantium
Next Generation of Bioplastic
―Building Blocks"
…………………………..……………………………………………………………………………………………….

70. Monomers / Intermediates from Vegetable Oils
Glycerol
Acrylic acid (Arkema)
Propane, 1,2 diol (ADM)
Soy based polyols (Dow, Cargill)
Castor oil / 12 hydroxy stearic acid (India)
Amino undecanoic acid (Atofina)
Next Generation of
Bioplastic ―Building Blocks"
……………...………………..……………………………………………………………………………………………….

71. The Future For Bioplastics Will Depend On
Oil pricing continuing to increase.
Expanding from Single-Use Compostable to Durable Applications.
Transitioning from Oil-Based to Renewable Feedstocks.
Addressing Issues:
– Sociological, Environmental & Political.
Composting/Recycling Infrastructure Developments.

72. Thank You