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