Introduction To Bioplastics
Dr. Jim Lunt
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
Basic Definitions for Bioplastics
Terminology
Standards
Measurements
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.
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.)
Embrittlementbegins
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)
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
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
Measurement of Biobased Content
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) PlasticsFocus is on ―end of life or disposal.‖
Independent of Carbon Source StandardsEN 13432 and ASTM D6400.
These two classes are, however,not mutually exclusive.
Biobased & Biodegradable
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.
Renewable resource versus oil based.
Reduced environmental impact.
Concerns about human health.
End-of-Life disposal issues – Landfill.
Legislative initiatives.
Drivers for Bioplastics
Oil Versus Corn Price
Courtesy Gevo
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 / m3and a barrel is 0.159 m3 it would be 134 kg or 295.4 lbsA 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 = 65Weight of a bushel = 56#
Cost of corn based carbon example $3.50/(56*0.65*0.4) =$0.240
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
Hull & Fiber
(23%)
•
Starch
(65%)
Germ
(7%)
Gluten Meal
(5%)
Fructose for
Sweeteners
Dextrose for
Fermentation
Feedstocks
Number 2 Yellow Dent is used in the USA for Lactic Acid Production
Corn as A Feedstock
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
White Pollution-China
Increasing Litter Concerns
Health Concerns
Legislation Against Petroleum Based Plastics
Japan Government has set a goal that 20% of all plastics consumed in Japan will be renewably sourced by 2020.
GermanyBan 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.
NetherlandsImplementing a 40 euro cents/kg tax on PET vs. tax on PLA of 8 euro cents/kg.
USAFederal 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
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?
How Do We Really Measure Sustainability?
Life Cycle Analysis - One attempt to measure sustainability.
Complex and Inputs/Outputs still Debated
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.
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
kg
CO
2 e
q. / k
g In
ge
o
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
50.2
27.235.2
69.6
77.885.6
0
10
20
30
40
50
60
70
80
90
2005 2006 2009 ACC Plastics
Europe
Gabi
PEA
MJ
/kg
In
ge
o
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
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
Projected Biomaterials Trends
GlobalDemand
for bioplastics will increase more than fourfold to
900,000 tonnes in
2013.
(Freedonia)
Projected Biomaterials Trends
Global Production
of bioplastics will increase
sixfold to
1.5 million tonnes
by 2011.
up from 262,000 tonnes in 2007.
(European Bioplastics)
GlobalDemand
for bioplastics will increase more than
fourfold to
900,000 tonnes in
2013.
(Freedonia)
Projected Biomaterials Trends
ProductionCapacity
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)
GlobalDemand
for bioplastics will increase
more than four fold to
900,000 tons in 2013.
(Freedonia)
Projected Biomaterials Trends
Bioplastics will still only be 1% of the approximate 230 million tons
of plastics in use today.
Projected Biomaterials Trends
The Evolving Biobased Plastics Landscape
Biobased Polymer CapacitiesFor 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
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?
CompoundedBiobased Compostable
O
OHHO
H CH3
L-Lactic Acid
O
OHHO
H3CH
D-Lactic Acid
(0.5%)
Polylactic Acid (PLA)
100% Renewable & Compostable
Key Compostable Bioplastics
Starch/PLA/ECOFLEX
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Compostable BioplasticsSecond Generation
Poly Hydroxy Alkanoates(PHA’s
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.
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 to119 million tons.
*http://soynewuses.org/downloads/reports/DisposalblePlasticsMOS.PDF
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 shrinkwrap.
Translucent cast and blown film for:
Trash bags Yard & GardenIndustrial refuse Kitchen and otherNewspaper 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.
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)
Major Concerns with Bioplastic Films
• Cost / lb. and density v polyethylene /polypropylene.
• Lack of curbside collection and municipalcomposting infrastructure.
• Poor tear propagation.
• Moisture sensitivity for starch based products.
• Controlled degradation times for mulch films.
• Barrier (moisture transmission) for starch and PLAformulations.
• Low temperature resistance of PLA unlessorientated.
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
Biaxially Orientated PLA
Cellulose Acetate
Compounded PLA/Starch Blends
BraskemDow/CrystalsevDuPontArkemaBASFRohm & HaasDow, CargillNatureWorks LLC
HDPE, LLDPE, PPHDPEPTT; PBT; Nylon 6,12Nylon 11,Pebax Nylon 6,10AcrylicsSoy based urethanes PLA Blends
Degradable
Tomorrow’s Biobased Leaders
Durable
NovamontNatureWorksMetabolixDSM
Origo BioPLA PHA’sPHA’S
………………………………………………………………………………………………………………………
………………………………………………………………………………………………………………………WHO? WHAT?
Continuing lack of infrastructure for useand disposal of compostable plastics.
Many biobased plastics players too focused oncompostability as the key differentiating asset.
Increasing demand for biobased, semi-durableand durable products for household goods,electronics and automotive applications.
Increasing interest and developments in existing and new monomers from renewable resources.
Why The Change?
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
Durable Applications are a Reality
Disposables Durables
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 MeetThe Needs for Durables
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Will Biopolymers Follow the Traditional Path to Maturity?
BASE POLYMER
ADDITIVESFillers/Fibers, Pigments
Lubricants, Mold release agents
MODIFIERSImpact modifiers, Rheology
modifiers, Plasticizers, Nucleating agents
BLENDSRigid/Flexible
Low/High Temp
COPOLYMERSChemical Res., High Heat
Ductility
Will Biopolymers Follow the Traditional Path to Maturity?
BASE POLYMER
(PLA)
ADDITIVESTalc, Kenaf
MODIFIERSAcrylics, Joncryl,
Citroflex, EBS
BLENDSPLA / Ecoflex PLA / PHBV,
PLA / PC
COPOLYMERSIsosorbide2,5 FDCA
PTT / Nylon 11 Bio Analogs
How Will Bioplastics Meet FutureDurable Products Needs?
General trends
How Will Bioplastics Meet FutureDurable Products Needs?
• Short Term (1-3years) – Blends of present generation bioplastics & blends with petro-basedplastics (PP, acrylics, polyamides )
General trends
How Will Bioplastics Meet FutureDurable Products Needs?
• Short Term (1-3years) – Blends of present generation bioplastics & blends with petro basedplastics (PP, acrylics, polyamides )
• Medium Term (3-5 years) – Blends of existing bioplastics with other biobased plastics (PTT, nylon 6,10, PBS)
General trends
How Will Bioplastics Meet FutureDurables Products Needs?
• Short Term (1-3years) – Blends of present generation bioplastics & blends with petro basedplastics (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)
Improved temperature performance over PLA.
Improved processing window over PHBV.
Wider mechanical property spectrum.
Almost completely renewable-resource based.
Still compostable.
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
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
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
PHBV/PLA Blended Product
Succinic Acid
THF1,4-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
L-KetalsHO
OH
O
O
succinic acid
HO OH
O
3-hydroxypropionic acid
OH
O
NH2
HO
O
glutamic acid
aspartic acid
OHHO
O
O NH2
HO OH
OH
glycerol
O
OHO
4-hydroxybutyrolactone
itaconic acid
HOOH
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
HOOH
OH
OH
OH
OH
O
O
glucaric acid
OO
HO
O
OR
*R=H, alkyl
New Biobased Materials In Development
Thermoplastics
Products and Markets
L-Ketals
Plasticizers Polyols
AdhesivesSolvents
IsobutyleneIsobutanol
Xylenes and
other aromatics
terephthalic acid
PET
other polymers
Isooctene
Courtesy Gevo
Biobased TPA For PET Under Development
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
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"
…………………………..……………………………………………………………………………………………….
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"
……………...………………..……………………………………………………………………………………………….
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.
Thank You
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