Introduction To Bioplastics

Dr. Jim Lunt

Presentation Outline
Basic Definitions for Bioplastics. Drivers for Bioplastics. Growth Projections and Market Trends. The Evolving Biobased Landscape. Performance Issues for Todays Bioplastics. Emerging Technologies. Conclusions.

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.)

Biodegradation Mechanism For PLA (In Compost At 60oC)

Num. Avg. Mol. Wt. (Mn)
70,000

% CO2 Evolved
100

80 50,000 Embrittlement begins % CO2 40 Mn 10,000 10 Polymer Hydrolysis

0

60

30,000

Complete Fragmentation
20 Time (Days)

20 0

30

40

Lactic acid and Oligomers Biodegradation

USDA Definition of Biobased Products

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.

Measurement of Biobased Content

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

Biobased & Biodegradable

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.

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.

Drivers for Bioplastics

Renewable resource versus oil based.

Reduced environmental impact.

Concerns about human health. End-of-Life disposal issues Landfill. Legislative initiatives.

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 / 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

100.00

Oil Versus Corn Price

Cost of Carbon Oil v Corn Sugar
$Oil/barrel

4.90
4.40

90.00 80.00
70.00 60.00 50.00 40.00 30.00 0.05

$Corn/Bu 3.90 3.40

2.90 crude oil cost corn cost 2.40

1.90
1.40 0.35 $Carbon Cost

0.15

0.25

Corn as A Feedstock
Starch (65%)
Fructose for Sweeteners

Gluten Meal (5%)

Dextrose for Fermentation Feedstocks

Hull & Fiber (23%)

Germ (7%)
Number 2 Yellow Dent is used in the USA for Lactic Acid Production

Net Corn Pricing Calculation

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.

White Pollution-China

Increasing Litter Concerns

Health Concerns

Legislation Against Petroleum Based Plastics

Key Legislative Initiatives for Bioplastics

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.

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.

5 4.5 4 3.5 3 2.5 2 1.5 1 0.5 0

Ingeo

PET
3.49 2.52 3.49

kg CO2 eq. / kg Ingeo

2.02 0.75 0.27 2005 2006

With REC

2009
Technology Improvements

ACC

Plastics Europe

Gabi PEA

Source Data: Ingeo - NatureWorks LLC ;

PET: M. Binder, Technical Director, PE Americas;

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

Cradle-to-Pellet Primary Non-renewable Energy Use

90 80

Ingeo
69.6 50.2 35.2 27.2

PET
77.8

85.6

MJ/kg Ingeo

70 60 50 40 30 20 10 0

2005
Source Data: Ingeo - NatureWorks LLC ;

2006
With REC

2009
Technology Improvements

ACC

Plastics Europe

Gabi PEA

PET: M. Binder, Technical Director, PE Americas;

Compared to any of the PET data sets, all of the Ingeo profiles have a lower non-renewable energy use
PLA: Vink E.T.H. et all

But There Are Other Issues

The Food versus Fuel Debate:
Food Crops V Biomass The Ripple Effect

Use of GMO's
End-of-Life disposal options:
Compostability Recyclability

Projected Biomaterials Trends

Projected Biomaterials Trends

Global Demand 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

Global Demand for bioplastics will increase more than fourfold to

900,000 tonnes in 2013.

(Freedonia)

1.5 million tonnes by 2011.

up from 262,000 tonnes in 2007.
(European Bioplastics)

Projected Biomaterials Trends

Global Production of bioplastics will increase six fold to Production Capacity of bio-based plastics is projected to increase from 360,000 tons in 2007 to about

Global Demand for bioplastics will increase more than four fold to

900,000 tons in 2013.

(Freedonia)

1.5 million tons by 2011.

up from 262,000 tonnes in 2007.
(European Bioplastics)

2.3 million tons by 2013.

(European Bioplastics)

Projected Biomaterials Trends

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

The Evolving Biobased Plastics Landscape

Biobased Polymer Capacities For Major Players

Product PLA PLA Company Natureworks Hisun Location USA China Capacity/mt 140,000 5,000 Price/# 0.85-1.20 1.25

PHAs
PHBH PHBV Materbi

Metabolix
Meridian/Kaneka Tianan Novamont

USA
USA China EU

300/50,000 (2010)
150,000? 2,000 75,000

2.50-2.75
n/a 2.40-2.50 2.0-3.0

Cereplast
HDPE/LDPE /PP

Cereplast
Braskem

USA
SA

25,000 200,000 (2010)

1.50-2.50
0.80-1.00

The Biobased Leaders Today

WHO?

WHAT?

NatureWorks, Hisun Novamont Cereplast Dupont Tianjin Bio Green /DSM Tianan Biologic Metabolix

PLA Mater-Bi, Origo Bi Cereplast BIOMAX (PTT, Plantic) PHA PHBV PHA

Braskem

Green Polyethylene

Key Compostable Bioplastics

.

Starch/PLA/ECOFLEX

Polylactic Acid (PLA)

O HO OH HO OH H3C H D-Lactic Acid CH3 O

L-Lactic Acid

(0.5%)

Compounded Biobased Compostable

100% Renewable & Compostable

Compostable Bioplastics Second Generation

Poly Hydroxy Alkanoates (PHAs

Major Bioplastic Packaging Markets

Four Sectors showing significant growth:
1. 2.

Compostable, single-use, bags/films. Thermoformed products for food applications.

3.
4.

Gift cards.
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 to 119 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 shrink wrap. Translucent cast and blown film for: Trash bags Industrial refuse Newspaper and magazine wrap Agricultural mulch films Yard & Garden Kitchen and other Diaper back sheets

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 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.

Comparative Gas Transmission Properties

Resin PLA PET (OPET) HDPE OTR 38-42 3-6.1 130-185 WVTR 18-22 1-2.8 0.3-0.4 CO2 201 15-25 400-700

PP
Nylon 6 EVOH PVC

150-800
2-2.6 0.01-0.16 4-30

0.5-0.7
16-22 1.4-6.5 0.9-5.1

150-650
10-12

4-50

Biaxially Orientated PLA

Cellulose Acetate

Compounded PLA/Starch Blends

Tomorrows Biobased Leaders

WHO?

WHAT?

Durable

Braskem Dow/Crystalsev DuPont Arkema BASF Rohm & Haas Dow, Cargill NatureWorks LLC Novamont NatureWorks Metabolix DSM

HDPE, LLDPE, PP HDPE PTT; PBT; Nylon 6,12 Nylon 11,Pebax Nylon 6,10 Acrylics Soy based urethanes PLA Blends
Origo Bio PLA PHAs PHAS

Degradable

Why The Change?

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.

Projected Durables Growth

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)

Durable Applications are a Reality

Disposables

Durables

Compostable Bioplastics Do Not Meet The Needs for Durables

.. ... ...

Areas of Concern
PLA

Starch Blends Hydrolytic stability Distortion Temp Vapor Transmission Shelf Life

PHAS

Hydrolytic Stability

Hydrolytic Stability Shelf Life

Distortion Temp (amorphous)

Vapor Transmission Shelf Life Impact Resistance Melt Strength

Processability
Melt Strength Economics

Will Biopolymers Follow the Traditional Path to Maturity?

COPOLYMERS Chemical Res., High Heat Ductility BLENDS Rigid/Flexible Low/High Temp MODIFIERS Impact modifiers, Rheology modifiers, Plasticizers, Nucleating agents ADDITIVES Fillers/Fibers, Pigments Lubricants, Mold release agents

BASE POLYMER

Will Biopolymers Follow the Traditional Path to Maturity?

COPOLYMERS Isosorbide 2,5 FDCA PTT / Nylon 11 Bio Analogs

BLENDS PLA / Ecoflex PLA / PHBV, PLA / PC MODIFIERS Acrylics, Joncryl, Citroflex, EBS ADDITIVES Talc, Kenaf BASE POLYMER (PLA)

How Will Bioplastics Meet Future Durable Products Needs?

How Will Bioplastics Meet Future Durable Products Needs?

General trends
Short Term (1-3years) Blends of present generation bioplastics & blends with petro-based plastics (PP, acrylics, polyamides )

How Will Bioplastics Meet Future Durable Products Needs?

General trends
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)

How Will Bioplastics Meet Future Durables Products Needs?

General trends
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)

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

100%PLA 90%PLA/10%PHBV
2Minutes Deformed

80%PLA/20%PHBV 70%PLA/30%PHBV

12Minutes Not Deformed

60%PLA/40%PHBV 50%PLA/50%PHBV

Samples Held up to 12minutes at 100 C

COURTESY OF PETER HOLLAND BV

Heat Distortion Properties of PHBV/PLA Blends

Sample 100% PLA 90/10 80/20 70/30 Load MPa 0.45 0.45 0.45 0.45 HDT oC 52.0 53.4 54.5 54.6

60/40
50/50

0.45
0.45

63.0
66.3

Glass Transitions of PHBV/PLA Blends

1. 2. 10% PHBV / 90% PLA 20% PHBV / 80% PLA 45.2OC 34.0OC

3.
4. 5.

30% PHBV / 70% PLA

40% PHBV / 60% PLA 50% PHBV / 50% PLA

33.4OC
23.9OC 14.7OC

PHBV/PLA Blended Product

Other Chemicals and Polymers from Plant Sugars

Polyurethanes Polycarbonate/PBT Blends

Nylon 6 & 6,6 Hexanediamine

Polycarbonates
Aliphatic Polyesters

PBT

TPEs

Adipic Acid

N-Methyl Pyrolidone

1,4-Butanediol
New monomers

THF Solvents Crop Growth Promoters Salt Replacements

Succinic Acid

Plant Sugars

New Biobased Materials In Development

O HO O
succinic acid 3-hydroxypropionic acid

O OH HO OH HO

O OH NH2

L-Ketals
O OR

glutamic acid

O HO O NH2 O OH O
itaconic acid

OH

HO OH
glycerol

OH

HO O

O HO
O

aspartic acid

4-hydroxybutyrolactone

O HO

OH O
levulinic acid

O HO O

OH

2,5-furandicacboxylic acid

OH OH OH OH OH
xylitol

OH OH OH HO OH OH OH
sorbitol

OH OH OH OH OH O

*R=H, alkyl

glucaric acid

Products and Markets

Plasticizers

Polyols

L-Ketals
Adhesives
Solvents

Thermoplastics

Biobased TPA For PET Under Development

Isobutanol

Isobutylene

PET other polymers

Isooctene

Xylenes and terephthalic acid other aromatics

Courtesy Gevo

Other Durable Bioplastics Are Appearing

Polyethylene from Sugar Cane
Nylon 6 from Lycine

Acrylics from Sugar

Polyurethane Using Soy Based Alcohols Increasing Synergism with the Biofuels Initiatives

Next Generation of Bioplastic Building Blocks"

...

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)

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