1

NatureWorks Ingeo™ Polylactide:

Past, Present and Future

RC Bopp

NatureWorks LLC

Minnetonka, MN

IOWA STATE UNIVERSITY

BIOPOLYMERS & BIOCOMPOSITES WORKSHOP

August 14, 2012

2

• NatureWorks: Who we are and what we do

• Early History

• Bioplastics Value Proposition

• Ingeo EOL Value Proposition

• Further Look into the Future

Agenda

3

Who We Are . . .

• 1st world-scale

biopolymer producer

• Economies of scale to

compete in traditional

plastics markets

(140,000 MT capacity)

• Peer reviewed eco-profile (LCA)

• Global plastics & fibers customer

base

• Ingeo applications breadth across

many markets, geographies, and

retail applications

• Privately owned by Cargill Inc and

PTT Global Chemical

4

Our Customers

sugar (dextrose)

Plants

Carbon dioxide

and water

manufacturing

Where it comes from….natural plastic from plants, not oil

What We Do . . .

5

5

O

OH

OH

HO

CH2HO

OH

HO

OH

O

CH3H

O

OH

OH

O

CH2HO

O

n

Starch Dextrose

(Glucose)

Lactic Acid

Hydrolysis

O

O

O

CH3H

n

2

PLA

Chemical Processing

Polylactide Synthesis

6

6

D-Lactic Unit L-Lactic Unit

220o C

180o C

Creating a Family of Polymers

7

Early History of Polylactide Polymers

– Lactide monomer production described in 1912

– Polylactide production described in 1932 (W.H. Carothers et al.)

• Technology developed further by DuPont, with high molecular weight polymers in

1955, but technology appears to have been shelved

• First commercial application c.1972, with Ethicon Inc. development of resorbable

sutures (poly-lactide-co-glycolide)

– Resurgence of interest in 1980’s

• E.S. Lipinsky, “Chemicals from Biomass: Petrochemical Substitution Options”,

Science, 212, 1465-1471 (1981) (Battelle Columbus Laboratories)

• E.S. Lipinsky and R.G. Sinclair, “Is Lactic Acid a Commodity Chemical?”, Chem. Eng.

Progress (Aug. 1986)

– Cargill project started in 1989

– Commercial production in Blair, Nebraska Dec. 2001

8

By 1996 the field was heating up…. Company PLA capacity

(MM lb/yr)

Patent

activity

PLA approach Purity/ mol wt

control

Cargill (U.S.) 10 (100 MM lb/yr in

preliminary design phase,

not announced)

10 Ring opening

polymerization

Lactide distillation

Chronopol (US) 2 planned (1996) 56 Ring opening

polymerization

Crystallization/

melt crystallization

Shimadzu

(Japan)

0.2 22 Ring opening

polymerization

Lactide

crystallization,

solid state

polymerization

Mitsui Toatsu

(Japan)

2-20 planned 97 Direct

condensation

Solvent with water

removal

Neste OY

(Finland)

Not available 1 Direct

condensation

Reactive coupling

Adapted from D. R. Witzke Ph. D. thesis, 1997, Michigan State University

Capacity based on published news reports. Patent activity is worldwide published applications. Chronopol patents

assumed to include Battelle, EcoChem, Ecopol, and DuPont.

9

It has been a complex journey…..

Project begins

at Cargill

Pilot plant

(5 lb/hr)

Semi-works plant

(1,000 lb/hr)

JDA Dow

Chemical

Cargill Dow

Polymers, LLC (JV)

NatureWorks LLC

(Stand Alone JV)

Cargill acquires Dow’s

interest in NatureWorks

Blair, NE

(20,000 lb/hr)

Polysar

JDA

NatureWorks jointly owned

by Cargill and Teijin

Wholly owned

by Cargill

Blair, NE

(40,000lb/hr)

’89 ’90 ‘91 ’92 ’93 ’94 ’95 ’96 ’97 ’98 ’99 ’00 ’01 ’02 ’03 ’04 ’05 ’06 ’07 ’08 ‘09 ’10 ‘11 ‘12

.AmberWorks

JV w/ BioAmber

10

A Cycle of Innovation

Innovation:

People implementing new

ideas to create value.

Requires:

People using new knowledge

and understanding to

experiment with new

possibilities in order to

implement new concepts that

create new value.

Adapted from Joyce Wycoff, Innovation Network,

Thinksmart.com

New knowledge

Implement

concepts

Produce new

value/ products

Develop

New concepts

Experiment/

New possibilities

New understanding

11

0

100

N(P

rocess)

1984

1985

1986

1987

1988

1989

1990

1991

1992

1993

1994

1995

1996

1997

1998

1999

2000

2001

2002

2003

2004

2005

2006

2007

Priority year

Chart

Cycle 1.

’89 ’90 ‘91 ’92 ’93 ’94 ’95 ’96 ’97 ’98 ’99 ’00 ’01 ’02 ’03 ’04 ’05 ’06 ’07 ’08 ‘09 ’10

Cycle 1. (1989-1995)

Development of basic monomer

properties, polymer properties,

technology to purify lactide and to

control polymer molecular weight,

melt point, and stability.

Process technology developed.

Culminates in products available

for market development.

Development of processes

has initial peak in 1993-

1996, NatureWorks is

actively filing at same time.

Project begins in

Cargill

Pilot plant

(5 lb/hr)

Semiworks plant

(1,000 lb/hr) JDA Dow

Chemical

Blair, NE

(20,000 lb/hr)

Blair, NE

(40,000 lb/hr)

12

0

100

200

300

400

500

N(E

nd-U

se)

1984

1985

1986

1987

1988

1989

1990

1991

1992

1993

1994

1995

1996

1997

1998

1999

2000

2001

2002

2003

2004

2005

2006

2007

Priority year

Chart

Cycle 2.

Cycle 2. (1996-2002)

Market development quantities of

IngeoTM are available. Polymer is

processed on commercial scale

lines. Process control and

manufacturing strategy are

refined. Culminates in design and

construction of full scale

manufacturing plant at Blair,

Nebraska.

Development of end

use applications

expands explosively,

peaking in 2000-2002.

Project begins in

Cargill

Pilot plant

(5 lb/hr)

Semiworks plant

(1,000 lb/hr) JDA Dow

Chemical

Blair, NE

(20,000 lb/hr)

Blair, NE

(40,000 lb/hr)

’89 ’90 ‘91 ’92 ’93 ’94 ’95 ’96 ’97 ’98 ’99 ’00 ’01 ’02 ’03 ’04 ’05 ’06 ’07 ’08 ‘09 ’10

13

0

100

200

300

400

500

600

700

800

N(P

roduct)

1984

1985

1986

1987

1988

1989

1990

1991

1992

1993

1994

1995

1996

1997

1998

1999

2000

2001

2002

2003

2004

2005

2006

2007

Priority year

Chart

Cycle 3.

Cycle 3. (2003-2010)

IngeoTM available in standard

grades. End products are

developed and moved into retail.

New compositions, copolymers,

flow additives, color packages,

nucleants, inhibitors, etc. being

developed worldwide. New

investments in processing

equipment opens bigger markets*

and achieves economy of scale.

Development of new

products such as

copolymers,

compositions,

modifiers of all types

continues to expand.

*Historically, new polymers have averaged 11 yrs to reach

300 MMlb/yr sales from when commercial plant was

operational. C. Musso, Ph.D. (McKinsey)

Project begins in

Cargill

Pilot plant

(5 lb/hr)

Semiworks plant

(1,000 lb/hr) JDA Dow

Chemical

Blair, NE

(20,000 lb/hr)

Blair, NE

(40,000 lb/hr)

’89 ’90 ‘91 ’92 ’93 ’94 ’95 ’96 ’97 ’98 ’99 ’00 ’01 ’02 ’03 ’04 ’05 ’06 ’07 ’08 ‘09 ’10

15

Cycle 4. A Quick Look at What’s New & What’s Next

‘08 ‘09 ‘10 ‘11 ’12 ’13 ’14 ’15 ’16 ’17 ’18 ’19 ’20 ’21 ’22 ’23 ’24 ‘25 ‘26 ’27

New knowledge

Implement

concepts

Produce new

value/ products

Develop

New concepts

Experiment/

New possibilities

New understanding

New knowledge

Implement

concepts

Produce new

value/ products

Develop

New concepts

Experiment/

New possibilities

New understanding

New knowledge

Implement

concepts

Produce new

value/ products

Develop

New concepts

Experiment/

New possibilities

New understanding

New knowledge

Implement

concepts

Produce new

value/ products

Develop

New concepts

Experiment/

New possibilities

New understanding

New knowledge

Implement

concepts

Produce new

value/ products

Develop

New concepts

Experiment/

New possibilities

New understanding

New knowledge

Implement

concepts

Produce new

value/ products

Develop

New concepts

Experiment/

New possibilities

New understanding

Our collective journey to a sustainable future.

New players enter PLA field

Production becomes global

Full complement of biobased

additives/ modifiers

Stereocomplex available in

market development quantities

Pilot development of 2nd

generation biopolymers and

biobased chemicals

Recycle infrastructure developed

and organics collection/

composting becomes widespread

Children today are in college and

in the workforce, innovating even

better ways to a sustainable

future.

Cellulosic feedstock in use at

commercial scale

Biorefinery campus, with multiple

ventures. On-site cogeneration,

minimal waste.

16

Environmental (consumer, retail, brand owners)

• Lower carbon footprint, less energy usage

• Better end-of-life options (litter, landfill, incineration)

• Target: lower environmental footprint of plastics

• Oil vs. plants feedstock cost (stability)

• Carbon or waste taxation

• Target: create viable alternate product portfolio (plastics)

Economic (plastics value chain)

Value Drivers

for the Industry

Even in these

extraordinarily difficult

economic times, the

STRATEGIC

and

ENVIRONMENTAL

value drivers remain

strong

“A SIGN OF THE TIMES”

• Renewable feedstock vs. oil

• Reduce dependence on foreign oil

• Target: cellulosic bio-refinery concept (gas + plastics)

Strategic (governments)

17

Review process

for new Eco-Profile

1. Publication in the Industrial Biotechnology

Journal, August 2010.

- Manuscript reviewed by several reviewers

- Update of our 2007 publication

2. Peer review by Dr. Ian Boustead of Boustead Consulting.

- Final report now available

3. Review by Dr. Alberta Carpenter of NREL followed by uploading the eco-profile as well as a process description into the US LCI database

Download:

- Spreadsheets with the data files

- Report giving description of Ingeo production process

Ingeo™ Technology Credentials

www.nrel.gov/lci

18

138

120

113

80

77

73

59

50

42

35

87

82

0 20 40 60 80 100 120 140 160

Nylon 66

Nylon 6

Polycarbonate

PS (HIPS/GPPS Avg)

PET (SSP)

PET (amorphous)

LD Polyethylene

Polypropylene

PVC (suspension)

Ingeo 2005

Ingeo 2009 CIT (current tech)

Ingeo Target

From cradle to polymer factory gate

[MJ / kg polymer]

-50% Greenhouse Gases Greenhouse Gases Non-renewable energy use

7.9

9.1

7.6

3.2

2.1

1.9

1.9

2.0

1.3

0.8

3.4

3.4

0 1 2 3 4 5 6 7 8 9 10

Nylon 66

Nylon 6

Polycarbonate

Polystyrene (HIPS/GPPS Avg)

PET (SSP)

PET (amorphous)

LD Polyethylene

Polypropylene

PVC (suspension)

Ingeo 2005

Ingeo 2009 CIT

Ingeo Target

From cradle to polymer factory gate

[kg CO2 eq. / kg polymer]

-60%

Continuous improvement process

Ingeo 2005 Ingeo Current Ingeo Target

-50%

7.9

9.1

7.6

3.2

2.1

1.9

1.9

2.0

1.3

0.8

3.4

3.4

0 1 2 3 4 5 6 7 8 9 10

Nylon 66

Nylon 6

Polycarbonate

Polystyrene (HIPS/GPPS Avg)

PET (SSP)

PET (amorphous)

LD Polyethylene

Polypropylene

PVC (suspension)

Ingeo 2005

Ingeo 2009 CIT

Ingeo Target

From cradle to polymer factory gate

[kg CO2 eq. / kg polymer]

-60%

Greenhouse Gases Non-renewable energy use

Value drivers:

Economic Strategic

Environmental

19

April 26, 2012 - OBAMA

ADMINISTRATION

UNVEILS “BIOECONOMY

BLUEPRINT” ANNOUNCES

NEW R&D INVESTMENTS

“The world is shifting to an innovation economy

and nobody does innovation better than America.”

—President Obama, December 6, 2011

“Decades of life-sciences

research and the development

of increasingly powerful tools

for obtaining and using

biological data have brought us

closer to the threshold of a

previously unimaginable future:

“ready to burn” liquid fuels

produced directly from CO2, …

plastics made not from oil but

from renewable biomass . . .”

Strategic (governments)

20

Strategic (governments)

21

2012 & Beyond: NatureWorks Looking Forward

Broadening Products

& Applications

Globalizing the

Manufacturing Platform

Monetizing the EOL

Value Proposition

Cellulosic

Feedstocks

22

Blair, NE

Rayong Province, Thailand

2015 target: Ingeo bioresin structurally less expensive than PS (and PET)

In 2015 NatureWorks will have 2 Ingeo plants operational

– Supported by 3 feedstock sources (corn, sugar cane, cassava)

– Stronger global commercial organization

Rayong Province, Thailand

Blair, NE

Rayong Province, Thailand

23

NatureWorks

Ingeo

Polylactides

Ingeo

Lactides

8000 Series - foam

7000 Series – ISBM Bottles

6000 Series – fibers/nonwovens

4000 Series - films

3000 Series – Injection Molding

2000 Series - Thermoforming

A comprehensive platform of

polymer grades with world

scale economies

Now offering polymer grade

Ingeo lactides to support further

global growth of the industry

To . . .

Broadening from

Ingeo

Polylactide

Lactic

Acid Lactide

Cost effective Ingeo production is via

the Ingeo lactide intermediate

Broadening Products

& Applications

24

Food Serviceware

Nonwovens / Fibers

Rigids Films

Durables

Where we are in the Market

Lactides Bus. Dev.

25

High-Heat Ingeo™ Hot Cup Lids High-Heat Ingeo™ Cutlery

International

Paper StalkMarket US Biopolymers StalkMarket

Ingeo™ High-Heat Technologies -

Food Service-Ware

26

Biaxially Oriented Films Growth

• Taghleef Industries

successfully starts

production of NATIVIA™

• NATIVIA™ is based on

Ingeo™, and is 100%

made from renewable

resources

• NATIVIA™ is a

compostable film that

complies with EN13432

27

iTunes Sony Bank, Inc. REI DaiNippon,

Mitsubishi Plastics

and Sony

Ingeo™ Based Card Technology

28

Bormioli Vedat

Injection Stretch Blow Molded Technology

Extrusion Blow Molded Technology

Shiseido Shampoo Bottle Polenghi Lemon Juice Bottle

29

Ahlstrom Huggies Elements

Naturals

Fibers / Nonwovens

GroVia

30

Max Jenny Dave Andersen Hernandez Cornet

Apparel

31

Ingeo in Japan

32

LG Hausys zea® Wall Paper

0.2(T) x 1,060(W) × 15M(L)

Structure

Application

Roll type

-. Residential

-. Commercial

Print

Backing

Paper

Ingeo

Ingeo in Korea

33

Dent, scratch

resistant

No color change

by environmental

Eco-friendly

9.0(T) x75(W) × 900(L)

Water Resistant

Plywood

Ingeo Laminate

Structure

Application

Yellow Soil

Adhesive

-. Residential

LG Hausys, zea® Flooring, “Prestige” line

Ingeo in Korea

34

• NatureWorks: Who we are and what we do

• Early History

• Bioplastics Value Proposition

• Ingeo EOL Value Proposition

• Further Look into the Future

Agenda

35

End of Life Options

Incumbent

Plastics Ingeo™

Landfill

X X

Recycle

X X

Incineration

X X

Compost

X

Anaerobic

Digestion X

Feedstock

Recovery X

Food

Scraps

12.7%

Paper

31.0%

Glass

4.9%

Metals

8.4%

Plastics

12.0%

Wood

6.6%

Yard

trimmings

13.2%

Other

3.5%

Rubber,

leather &

textiles

7.6%

Total US MSW Generation (by material), 2008

250 Million tons (before recycling)

Source: Municipal Solid Waste in the US: 2008 Facts & Figures

Progressing New

After-Use Options 31.8 MM tons/year

Methane (x23 CO2) release in landfill

Food waste diversion:

From landfill to composting facility

36

Paper

31.0%

Glass

4.9%

Metals

8.4%

Plastics

12.0%

Wood

6.6%

Yard

trimmings

13.2%

Other

3.5%

Rubber,

leather &

textiles

7.6%

Food

Scraps

12.7%

Total US MSW Generation

(by material), 2008

250 Million tons (before recycling)

Source: Municipal Solid Waste in the US:

2008 Facts & Figures

Plants

A Credible Closed Loop Solution

Exists Today In Seattle…

RENEWABLE ► SUSTAINABLE ► END-OF-LIFE ► COMPOST

End-of-Life Options

And Opportunities

37

End of Life Options

Incumbent

Plastics Ingeo™

Landfill

X X

Recycle

X X

Incineration

X X

Compost

X

Anaerobic

Digestion X

Feedstock

Recovery X

Food

Scraps

12.7%

Paper

31.0%

Glass

4.9%

Metals

8.4%

Plastics

12.0%

Wood

6.6%

Yard

trimmings

13.2%

Other

3.5%

Rubber,

leather &

textiles

7.6%

Total US MSW Generation (by material), 2008

250 Million tons (before recycling)

Source: Municipal Solid Waste in the US: 2008 Facts & Figures

Progressing New

After-Use Options

30 MM tons/year

< 10% recycled (some PET bottles only)

Closed loop recycling vs. today’s

bottle ► package ► landfill

38

Ingeo is a bio-polymer made from lactic acid

Ingeo

Polylactide

O O

O

O

O O

O

O H

H

Lactic Acid

Polymerization

Hydrolysis

A new paradigm for Cradle-to-Cradle materials recycle . . .

“Feedstock Recovery”

39

• COP 15 main conference area:

Ingeo™ used in main hall carpeting

and Food Serviceware

• New Company, BIOCOR LLC, launched with a business

model founded on trading post consumer PLA in any format . .

.

Monetizing the EOL

Value Proposition

40

• Who we are and what we do

• Early History

• Bioplastics Value Proposition

• Ingeo in the Market Today

• Ingeo 3801X

• Ingeo EOL Value Proposition

• Further Look into the Future

Agenda

41

Latest Ingeo Business & Product Developments

• Extending the Ingeo Product / Applications Range

1. Ingeo Lactides

2. New High % L (> 0.3%D) Performance Grades

3. NatureWorks - BioAmber

Joint Venture

4. Arkema’s Rnew –

Partnering to produce

bio-based (& improved) Plexiglas

42

Ingeo Platform Extension

Ingeo Platform: “Performance materials from renewable resources”

L-100 Lactide

L-300 Lactide

L-800 Lactide

M-3000 Lactide

Lactide

monomer platform

Family of

Monomers

43

Ingeo Platform Extension

3 series Injection Molding

7 series ISBM – bottles, BM

6 series Fibers, Nonwovens

4 series Films, cPLA

2 series Thermoforming

8 series Foam

1st Gen (Lactic)

polymer platform

Ingeo Platform: “Performance materials from renewable resources”

Family of

Polymers

L-100 Lactide

L-300 Lactide

L-800 Lactide

M-3000 Lactide

Lactide

monomer platform

Family of

Monomers

3100 HP

3260 HP

6100 D

6260 D

Family of

High % L Polymers

44

High % L Performance Polymers

Improved Nonwovens

• Reduced shrinkage and improved dimensional

stability

• Increased hydrolysis resistance

• Capable of higher heat set temperatures

• Higher Tm creates advantages in bi-

component systems

• Larger processing windows

Improved Durables

• Faster cycle times & higher production rates

for lower molded part cost

• 3-4x increase in bulk crystallization rate

• 15°C improvement in heat deformation

temperature vs traditional Ingeo grades

• ~30% higher modulus above Tg

• Increased hydrolysis resistance

45

“Elongation”

“S

tiff

ne

ss”

Bio-based

Conventional Plastics

PET

PP

PS Starch

Lactic Acid based polymers

PE

Succinic Acid based polymers

Performance Properties

New compounded Ingeo grades

combining properties of succinic

and lactic acid polymer platforms

Broadening the Addressable

Ingeo Property Window

46

Slide 46 ITR, February 2012

• Global commercial presence

• Established Ingeo customer

relationships

• Applications development

experience

• Breadth of markets

• Experience in commercializing

new-to-the-world polymers

• Novel resin compounding

intellectual property

• Award-winning biotechnology

• Renewable chemicals

delivering high performance,

low carbon footprint, cost

competitive, building blocks

The Joint Venture combines the best of both companies into an

entity tasked with developing a new family of bio-based

compounded Ingeo polymers

Basis of the JV

Partnership & Synergy

47

New Developmental Grades Resulting from the JV

• Thermoforming

Grade

– Ingeo AW 240D

• Injection Molding

Grade

– Ingeo AW 300D

48

Arkema’s Ingeo-based Plexiglas® Rnew resins

• Compounded alloys of Arkema / Altuglas

International’s PMMA and NatureWorks’ Ingeo

(durable product focus) Provide step change in impact performance (≈ PETG, PC)

Significant increase in chemical resistance ( > PC)

Drastic increase in processability

Reduced carbon footprint & cost

- All whilst incorporating bio-sourced

materials … without compromising

optics, scratch resistance, color

acceptance or surface aesthetics

48

49

0

20

40

60

High impact

PMMA

Impact

PMMA

10%PLA

Impact

PMMA

20%PLA

Impact

PMMA

40%PLA

Impact

PMMA

60%PLA

PETG PC

Imp

act str

en

gth

(J)-

Multi-axial impact

• Formulation design allows for tailored solutions

• Extraordinary improvements in impact strength while maintaining

modulus and strength

• Impact performance comparable to PETG and PC

Acrylic

Acrylic / Ingeo Alloys PETG

PC

Synergistic Impact Modification Effect

Source: Altuglas International a subsidiary of Arkema International

Arkema’s Ingeo based Plexiglas® Rnew resins

50

Cellulosic

Feedstocks

Where we are

Where we’re going

– Our footprint is small: At full capacity, Ingeo™ represents:

• < 0.2 % of 2007 US corn production (< 0.05 % of global corn production)

– Ingeo technology is feedstock Agnostic. 2nd plant will use most

abundant local industrial sugar or starch source

– 2nd Generation is becoming an industrial reality

51

Abengoa - Spain Myriant - Louisiana

Verenium - Louisiana • US government strongly supports

cellulosic bio-refinery concept

• Various feedstocks being evaluated

• Questions:

• Timing of first bio-refineries?

• Economics of bio-refineries?

Switching from 1st to 2nd generation feedstock will be as

much an economic as an environmental decision

Cellulosic

Feedstocks

52

Biopolymers are here to stay . . .

• Meet a strategic need to shed our oil addiction

• Meet a strategic need to lower our carbon footprint

• Meet global consumer expectation for sustainability without sacrifice

Biopolymers are no longer “embryonic” (Translation: hard to get, hard to use, very expensive)

Let the journey continue . . .

• New entries into the market place (partially Bio PET, Bio PE, PHA)

• Feedstock diversification

• Economies of scale (resin, converters)

• Recycling infrastructure

Keeping innovation going

Broadening Products

& Applications

Globalizing the

Manufacturing Platform

Monetizing the EOL

Value Proposition

Cellulosic

Feedstocks

Summarizing Comments:

53

53

Acknowledgements:

-Dr. Jeff Kolstad

-Steve Davies

-Andrea Ziadi

-Lisa Moore

-Julie Sobon

54

54

55

Thank you!

Richard_C_Bopp@NatureWorksLLC.com

www.natureworksllc.com