DuPont BioMaterials: Enzymatic polymerization - A new ... and functions in DuPont including product & technology development, ... POLYSACCHARIDE BASIC PROPERTIES ... Thermal …

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Biobased Performance Materials Symposium

15 June 2017, Wageningen, The Netherlands

Session 2

Presentation by: Christian Lenges, DuPont Industrial BioSciences

Title: DuPont BioMaterials: Enzymatic polymerization - A new process

for engineered polysaccharides

Author: Christian Lenges

Contact details:

Christian P. Lenges

DuPont Industrial BioSciences,

200 Powder Mill Road,

Experimental Station E356,

Wilmington 19803, DE,

USA

E [email protected]

Curriculum:

Christian Lenges, Business Development for BioMaterials in DuPont Industrial BioSciences,

focused on the development and launch of growth businesses to make industrially important

chemicals and materials from renewable feedstocks. He has experience in a variety of

businesses and functions in DuPont including product & technology development, portfolio

management & venture leadership. He has had leadership roles in DuPont’s efforts in

Biomaterials since 2008 in the Sorona® business, and in the biomaterial ventures driving

towards commercial launch.

Dr. Lenges holds a Diplom Degree from the Heinrich Heine University in Duesseldorf, and a

Ph.D. in Chemistry & Catalysis from the University of North Carolina at Chapel Hill.

Abstract:

DuPont Industrial BioSciences continues to lead the BioMaterials space by advancing the

development of new material platforms with differentiated performance and unique

customer value. Selecting winning project propositions and managing the complex path

from proof of concept demonstration to commercial launch has been key to creating growth

in the biomaterials space. Within this presentation, one program in the development

portfolio will be discussed in more detail.

Polysaccharides are important biopolymers with a wide range of industrial and consumer

product applications. Historically, structural polysaccharides such as cellulose have been the

backbone of early material science for applications in fibers, films and early thermoplastics.

DuPont Industrial Biosciences has developed a family of engineered polysaccharides ranging

in molecular weights, solubility, and polymer architecture. The underlying enzymatic

polymerization process offers the opportunity to design the polymer structure and the

material properties of these new biomaterials.

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. . . . . . . . . DuPont Industrial Biosciences | Name speaker

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NUVOLVE™ - ENGINEERED POLYSACCHARIDES: ENZYMATIC POLYMERIZATION - ENABLED POLYSACCHARIDES & APPLICATIONS June 14, 2017

Christian Lenges – DuPont Industrial BioSciences

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7/3/2017

INNOVATIVE

SCIENCE

HIGH

PERFORMANCE

SCALABLE

SUPPLY

ACCESSIBLE &

AFFORDABLE

RENEWABLE

SOURCING

RESPONSIBLE

BIOMATERIALS

RETHINK RENEWABLE PERFORMANCE DuPont Biomaterials takes cues from nature to create

eco-efficient renewable biomaterials that enhance the

performance of everyday products

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ADVANCING THE FUTURE OF INDUSTRY TO SERVE SOCIETY AND SAFEGUARD THE ENVIRONMENT

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DuPont Industrial Biosciences is working to reform the way we produce and consume

Renewable Agricultural

Resources Industrial Scale Conversion

Sustainable, High-

Performance Products

RENEWABLE SOURCES

Bio/chemical

transformation

Bio/chemical

transformation

BIOACTIVES

BIOMATERIALS

BIOFUELS

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We consider a range of important, inter-connected factors

when developing new biomaterials technology

“Sweet spot” for new

technology development

Economics

& Scalable

Supply Chain

Performance

& Consumer

Benefits

Environmental

& Social Impact

Value-in-use

Market

Relevance

and Accept-

ance

Market

innovation

Production

Capability

Economy

of Scale

Cost

Land Use

Farming

& Bio-

diversity LCA Data

End of Life

Treatment

Gen 1 vs.

Gen 2

Feedstock

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2/2017 6

Sources Matter

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THE STORY OF SORONA

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DUPONT INDUSTRIAL BIOSCIENCES: BIOMATERIALS

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A REVOLUTIONARY PARTNERSHIP = FDME BREAKTHROUGH

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THE NEXT BREAKTHROUGH IN BIOMATERIALS: LEARNING FROM NATURE

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Cellulose b(1,4) linkage

Starch α(1,4) linkage

INSPIRED BY NATURE

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Polysaccharides extracted from plants are widely used to provide unique end-use applications

but are limited by processes and raw material source. Nature often produces mixtures.

Xanthan Gum

Alginates Locust Bean Gum

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BIOMATERIAL PLATFORM INSPIRED BY NATURE

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Cellulose and starch are well known building blocks for natural based materials.

Alpha-1,3-glucan is a largely unexplored structural polysaccharide.

Cellulose: beta (1,4) linkage Starch: alpha (1,4) linkage alpha (1,3) linkage

Engineered Polysaccharide

O

OH

OH OH

OO

OH OH

OH

O

N

O

OH

OH OH

O

O

OH OH

OH

O

N

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ENGINEERED POLYMERS DIRECTLY FROM SUGAR

Using enzymatic polymerization to create a variety of polymer

structures with unique product features and application benefits

Linkage control: Selective polymerization of sucrose to polysaccharide

Structural control: Crystallinity, solubility – DPW & PDI Control

Process control to define polymer microstructure

POLYMER

CH2OH

H O H

OH

O

H

H

H

OH

O

CH2OH H O

CH2OH

H

O

H

H

OH

SUCROSE BIOCATALYST

PolySaccharide

Applications

Paper Coatings

Fibers & Fiber Additives

Composites

Packaging

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BIOPROCESS CONTROL: FROM MOLECULAR DESIGN TO POLYMER ARCHITECTURE & PARTICLE MORPHOLOGY

Platform Technology to Engineer New Raw Materials

MATERIAL

MORPHOLOGY POLYMER

ARCHITECTURE

Linear vs Branched

Structures

CH2OH

H O H

O

H

O

H

H

H

O

H

O

CH2OH H O

CH2O

H

H

O

H

H

O

H

SUCROSE ENZYMATIC

POLYMERIZATION

MOLECULAR

DESIGN

Linkage Control

Selective Functionalization

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BIOCATALYST – GLUCOSYLTRANSFERASE (GTF)

Highly conserved structure despite significant sequence diversity

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Signal peptide

Catalytic domain Glucan binding

domain

Variable

domain

GTF from S. mutans

NCBI database

Glycoside-Hydrolase family 70 (GH70)

Monomer with typical MW of 160 kDa

Extracellular enzymes, mainly produced by:

Streptococcus species

Leuconostoc species

Lactobacillus species

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NUVOLVE™ ENGINEERED POLYSACCHARIDES PATH TO COMMERCIAL REALITY

Key Status Highlights

• Advancing process, product & application development

• Targeting first commercial scale supply

• Ongoing pilot plant operations to supply first sales

• Development materials available

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POLYSACCHARIDE BASIC PROPERTIES – ALPHA 1,3-GLUCAN

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Typical Properties

Brightness 90 - 96

Degree of Polymerization 800 (400 – 1500)

PDI 1.7 - 2

Residual Sugars 0.1-1.0 wt%

Dry polymer solids > 88 wt%

Particle size distribution (d50) 10-30 µm

Primary Particle Size 10 – 30 nm

Overall Surface Energy 53 mJ/m2

Crystallinity Index ~ 50%

Bulk Density 1.5 kg/m3

o Water insoluble free flowing powder

o Zeta Potential essentially zero !

o Water absorption isotherm between cellulose I & II

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BIODEGRADABILITY ASSESSMENTS

ASTM D5511: simulates & accelerates biodegradation

process in landfill

Final biodegradation was 85% +/-1.0% or 105.0% relative

to reference cellulose

Conclusion: Considered completely biodegradable under

mesophilic anaerobic conditions.

High Solid Anaerobic Degradation

Under Mesophilic Conditions (37C)

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Soil Biodegradation Test

ISO 17556 Plastics: determines ultimate aerobic

biodegradability in soil

Final biodegradation was 85.6% +/- 0.3% or 104.4%

relative to reference cellulose

Conclusion: Fulfilled 90% requirement within 90 days of

testing under given aerobic conditions.

OWS

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POLYSACCHARIDE IN BIOCOMPOSITE APPLICATION EXAMPLES

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Engineered polysaccharides from DuPont show promising performance

results across multiple markets & applications. For example:

RUBBER COMPOSITES

THERMOPLASTIC COMPOSITES

HIGH SPEED INK JET COATINGS

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THERMOPLASTIC FILLER APPLICATIONS

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Spherical Particle in Powder Form (5-10 micron)

Efficiently Compounded into PP, PE, PLA, others

Maintains Mechanical Properties of Compounds

at high PolySaccharide load

Example 10% - 40% additive in PLA:

Tensile Modulus: 4000 +/- 500 [MPa]

Tensile Strength: 40 +/- 10 [MPa]

Whiteness & Low impurities

Thermal Stability

Less degradation byproducts

Low melt viscosity - even at high loads

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PLA / POLYSACCHARIDE COMPOUNDS

Target Injection Molding and Extrusion Grades

Assessment of Coupling Additives to Improve Thermal Stability

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Poly-

Saccharide %

Coupling

Additive

Yield

stress

(Mpa)

Notched

Izod (J/M)

Elongation

% HDT (C) Biocontent

0 - 50 27 <5 55-100 100%

20 - 55 35 5 - 8 67 100%

20 A 52 32 5 130 98%

30 A 48 32 5 130 98%

20 B 45 27 4.5 140 96%

20 C 45 41 15 140 90%

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PLA / POLYSACCHARIDE COMPOUNDS: BIODEGRADABILITY SYNERGIES

PolySaccharides Meet fundamental Biodegradability

Requirements across key certification categories

PLA/PolySaccharide Compounds with Synergistic Effect

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Engineered PolySaccharides

in biobased thermoplastics

Meeting biodegradability targets at high bio content

Improved performance Modulus, HDT, Color

Processability injection cycle time & throughput

06/May/2017

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TEM Images of Glucan polymer from Enzymatic Polymerization BioProcess: Primary Particle

BIOPROCESS CONTROL: FROM MOLECULAR DESIGN TO POLYMER ARCHITECTURE & PARTICLE MORPHOLOGY

CH2OH H O H

O

H

O

H

H

H

O

H

O

CH2OH H O

CH2O

H

H

O

H

H

O

H

SUCROSE PRIMARY

PARTICLE

ENZYMATIC

POLYMERIZATION AGGLOMERATES PARTICLE

AGGREGATES

Associated Glucan Chains 10-30 nm 100-300 nm 1000-5000 nm

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Key Requirements:

Compatibility with Rubber Formulations

Maintain or Improve Properties

Advancing Sustainability & Performance

Rubber/Filler Processing

Base Line Composites Results

Examples: Carbon Black & Silica Replacement

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Rubber

Filler

Reinforcing Materials

Plasticizers, Anti-ageing

Vulcanization Additives

Adopt to

Current Process

Compound

Processing

Rubber Raw

Materials

Match &

Advance on

Performance

End

Use

Markets

Tires

Belts

Hoses, Gaskets

Shoes etc

Curing

Process

Product

Forming Processes

NUVOLVE™ ENGINEERED POLYSACCHARIDES: REINFORCING FILLER APPLICATION OPPORTUNITIES

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ASSESSMENT IN TYPICAL RUBBER PROCESSING: COMPOUND DEVELOPMENT

Replace carbon black and/or silicas at various levels

Current coupling agents viable

Good wetting, homogenous, non-porous

Lower torque – Decrease in viscosity

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TEM images displays the dispersion polysaccharide – silica hybrid

reinforcing fillers in rubber compounds

- Effective dispersion in rubber composite

- No significant agglomeration of polysaccharide particles observed

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EXAMPLE: CARBON BLACK REPLACEMENT IN TIRE TREAD FORMULATIONS

Improvement of elongation & overall toughness

Tan delta (60C) of composites has improved

Rebound: increased at RT & decreased at 0°C

Lower density – 10-20%

Different grades of polysaccharide fillers

Surface area change

Lower particle size / higher surface activity

Improve abrasion / maintain Tan delta (60C)

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Compound Compatibility & Positive Impact on Dynamic Performance

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PTS MUNICH LAB-HIGH SPEED INKJET – PRINTER TEST UNIT

7/3/2017

The printing system is equipped with two

Industrial Oce/Canon print heads (piezo), and a wipe unit

Inks: pigment ink Oce black and cyan

Printing speed: up to 100 m/min

Wiping of 3 Data Matrix Codes after predefined drying time 1,7 seconds

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HSI Not wiped HSI Wiped

(1,7 s) Desk Jet

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GLUCAN CAN MAKE A SIMPLE COATED PAPER INK JET PRINTABLE

parameters Control

S4-HSI3 S4-HSI3.1

Coating Formulations

UF CaCO3 – 100

Starch - 15

UF CaCO3 – 70

Starch – 15

Glucan - 30

coating weight g/m² 8,1 8,3

coating thickness µm 5,4 7

printing test with HSI printer

wipe-test

after 1,7 sec 600 dpi A/F A/A

non wiped/wiped 900 dpi A/- A/C

1200 dpi A/- B/F

Printing Test with Desk Top Printer

Color Density Power Spectrum

Black/ Cyan

22.6

90

25.8

93.2

Mottle Index Power Spectrum

Black/Cyan

10.3

32.7

9.8

15

Less „smear“ due to faster ink absorption.

Better color density, dot gain and mottle

index.

HSI3

Reference

Glucan HSI 3

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HIGH SPEED INKJET – SEM HSI 3 (X 3000)

HSI 3 100 parts UF CaCO3 HSI 3.1 30 parts PSCC, 70 parts UF CaCO3

Polysaccharide Increases Porosity of Coating Enhancing Water Absorption

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NO LOSS IN QUALITY - REDUCTION IN SILICA AND BINDERS IN HIGH QUALITY IJ COATING

parameters Control S1-HSI1.4

Coating Formulations

Silica 1 – 75

Silica 2 - 18

--------------

PVOH – 34

PVAc – 50

Others - 17

Silica 1 – 50

Silica 2 – 18

Glucan – 25

------------------

PVOH – 34

PVAc – 40

Others -17

coating weight g/m² 6.1 6.2

coating thickness µm 18.3 19.1

printing test with HSI printer

wipe-test

after 1,7 sec 600 dpi A/A A/A

non wiped/wiped 900 dpi A/A A/A

1200 dpi A/F A/F

Printing Test with Desk Top Printer

Color Density Power Spectrum

Black/ Cyan

34.5

90

35.1

92.3

Mottle Index Power Spectrum

Black/Cyan

0.6

1.2

0.8

1.9

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Control Replace 25 parts Si

With Glucan

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NUVOLVE™ ENGINEERED POLYSACCHARIDES THROUGH ENZYMATIC POLYMERIZATION

New Class of Renewable

Material with Unique Properties

Key Processing Benefits

Rapidly Renewable, Regional

Feedstock

LCA, Land Use, Light Weighing

& Reduced Fuel Consumption

Advancing to Commercial

Reality

Multi ton quantities available for

Development

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THANK YOU FOR YOUR ATTENTION

Learn more about DuPont Biomaterials

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7/20/16

biosciences.dupont.com/biomaterials

@DuPontBiobased

DuPont

Copyright

Copyright © 2016 DuPont. All rights reserved. The DuPont Oval Logo and the Leaf Globe are trademarks or registered trademarks of

E. I.du Pont de Nemours and Company or its affiliates.

Nothing contained herein shall be construed as a representation that any recommendations, use or resale of the product or process

described herein is permitted and complies with the rules or regulations of any countries, regions, localities, etc., or does not infringe

upon patents or other intellectual property rights of third parties.

The information provided herein is based on data DuPont believes to be reliable, to the best of its knowledge and is provided at the

request of and without charge to our customers. Accordingly, DuPont does not guarantee or warrant such information and assumes no

liability for its use. If this product literature is translated, the original English version will control and DuPont hereby disclaims

responsibility for any errors caused by translation. This document is subject to change without further notice.

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DuPont BioMaterials: Enzymatic polymerization - A new ... and functions in DuPont including product & technology development, ... POLYSACCHARIDE BASIC PROPERTIES ... Thermal …